Chapter 5

CoordinationChemistryReviews,103 (1990) 1-161 ElaevierScience Publishers B.V., Amsterdam- Printed in The Netherlands

Chapter

5

ELEMENTS OF GROUP 5 D.B.Sowerby 5.1

2

NITROGEN .............................................. 5.1.1 5.1.2 5.1.3 5.1.4 5.1.5 5.1.6

2 4 7 10 10 12

Nitrogen-Nitrogen Bonds ........................... ................................... Bonds to Carbon Bonds to Oxygen ................................... ................................. Bonds to Halogens ......................... Bonds to Other Non-metals ................................... Bonds to Metals

14

PHOSPHORUS ..........................................

5.2 5.2.1 5.2.2 5.2.3 5.2.4 5.2.5 5.2.6 5.2.7

Phosphorus, Bonds to Bonds to Bonds to Bonds to Bonds to Bonds to ARSENIC

5.3 5.3.1 5.3.2 5.3.3 5.3.4 5.3.5 5.3.6 5.3.7

Polyphosphines and Phosphides ........................ Group 3 Elements ........................ Group 4 Elements ................................ Halogens ................................ Nitrogen Oxygen .................................. Selenium or Tellurium Sulphur,

5.4.1 5.4.2 5.4.3 5.4.4 5.11.5

........................ and Arsenide6 ........................ Boron or Gallium ....................... Carbon or Silicon ................................ Halogens ................................ Nitrogen Oxygen .................................. Selenium or Tellurium Sulphur,

Polyarsines Bonds to Bonds to Bonds to Bonds to Bonds to Bonds to

Antimonides Bonds to Bonds to Bonds to Bonds to

...................................... ....................... Carbon or Silicon ................................ Halogens Oxygen .................................. ..................... Sulphur or Selenium

BISMUTH .............................................

5.5 5.5.1 5.5&z 5.5.3

5.5.4 5.5.5

.................... Dibismuthines and Bismuthides Bonds to Carbon .................................. ................................ Bonds to Halogens Bonds to Oxygen .................................. ................................. Bonds to Sulp-hur

REFERENCES .................................................

0010-8545/90/$56.35

..........

Q

1990 ElaevierScience Publishers B.V.

14 28 30 59 65 83 97 105

.............................................

ANTIMONY ............................................

5.4

........

..........

105 108 110 115 116 118 120 121 121 122 125 129 130 132 132 133 133 134 135 137

5.1

NITROGEN

5.1.1

Nitrogen-Nitrogen

New

dinitrogen

Co(PMe,),(c-C&H,). with

magnesium

alkali

Bonds

cobaltates itself

on further

[(Et,O)RMgN,Co(PMe,),],. study

by reducing

which

reaction

is rapidly

porphyrin,

Ru(TMP1

with

reagents

give shown

taken

where

derivative

up by the

TMP

to contain

The

by

bridging

the diketone the

diazoalkane

initial

(RCNSNSN),,

where

(r, R = NCOPhl

Selective

complex containing

linkage

excitation

plasma,

when

in methanol

initial

ligand

It is also to both

at

protonation

[W(acacl(NNHl(PMe,Ph),I

elimination.

nitrogen

into the S-S

involves

to give

nitrogen

complex, in low yield

acetylacetone

of the diazenido

(NN=CMeCHZCOMel

In a low pressure

with

species

mono(dinitrogen)

results

mechanism

addition

and water

of 5,10.15,20-tetra-

of the related

is treated suggested

ruthenium

bistdinitrogenl

alkenyldiazenidotungsten

N, by acetylacetone

by nucleophilic

14-electron

is the dianion

the first

amount

A novel

[W(N,),(PMe,Ph),l 50°C. [31

to give

an

and Bu",

mer-[W(acac)(NNCMeCHCOMe)(PMe,Ph),l,

inserted

with

as

Crignard

to give

a small

compound.[Zl

convert

ligands,

are formulated

with

chloride

for R = Me, Ph. Me,CHCH2

on the t-butyl

mesitylporphyrin,

bonded

by treating

cobalt(II1

units.

Nitrogen

together

synthesised

of the appropriate

The compounds,

M[CoN,(PMe,l,l.

diazenide

been

obtained

in the presence

metal.111

an X-ray

have

followed

to a CO group possible

hydrazido

of

of

to

(NNH,)

and

species. a nitrogen

atom

is directly

of the bis(dithiadiazole1,

(RCNSSN),

R = Ph or p-C1C,H4.[41

(21

of the N=N JZ electrons

(31

in (11 leads

to the

3 intermediate the

first

stable

diradical

known

under

Attempts acids)

esters

by treating

Kz[S,C=NNHC(S)SMel of

(3).[51

iodide

gives

is

in the presence

bis(dithiocarboxylic

with

K2[SzCNHNHCSzl

or

hydrazine

with

Hydrazine

and carbon

of sodium

methoxide

to give

(RS),C:N.N:C(SR),.[61

(4-1 and

closure

The product

of 1,2-hydrazine

methyl

or by reacting

react

ring

atmosphere.

to prepare

oxysulphide

via subsequent

cycle-propapyridine

an argon

either

mixtures

(2) which

Cl(C(S)SEt

led to

N-N

II

II RS-c\S~C-sR (4)

hydrazine

bis(monothioformates1

converted

by methyl

turn

dithio-thiadiaxoles

give

Non-planar,

solid

[1,2-hydrazine esters.[81 gives

state

ester

compound

the N-N bond

R.CX.NH

the two halves

groups

with

its S,S'-

distance

of hydrazine

with

and O,O'-methyl methyl

iodide

results

when

thiocarbazate.

is 138.5pm

and although

the dihedral respectively,

with

Bu",SiClOLi

but the product

ButzSi(OLilNHNHSi(OLi)Bu'2

for potassium

isomer

are,

in

reagent.

O-methyl

are planar,

of the molecules

Reaction

104.5".

reported

salt

These

Lawesson's

and

the O-bonded

reacts

can be

esters.[71

are

the potassium while

methylxanthate

which

(4, R = Mel with

structures

of

Treatment

individual

to S.S'-dimethyl

bis(thiocarboxylatel1

the S-bonded

potassium each

iodide

Na,[SOCNHNHCOSI,

angles 78.8, leads

In the

relating 77.5

and

to

from methylhydrazine

is

MeNHNHSi(OHlBu',,[91 In the

1:l DMF adduct calcium

solution, groups

at ca. 240pm

similar

shared

The azide

axis. Zn-N-N

angles

structure groups

described

as common

are

pentagonal

azide.

by four

and two oxygens

coordination

previously

of calcium

is coordinated

pattern

ligand

found

and connected

group

is asymmetric

between

The

to give (N-N.

126.9 and

present

in Et4N[UOz(Nslsl,

shared

between

neighbouring

geometry.[l21

from

azide

molecules;[lOl

nitrogen

strings 116 and

130.4.

is also

bipyramidal

in aqueous atoms

a

in Zn(N,lz.2.5Hz0,

as a trihydrate.[lll

edges

varying

from

is also

obtained nitrogen

atoms

along 120pml

A chain

are

the b with

polymeric

where

two of the azide

metal

atoms

giving

The

related

(Me,N),[(UO,),-

4 (N,),Ol.H,O

contains

hexanuclear

[(lJOZ1~(Ns1160Zle-

I\

N

N /\

N,

5.1.2

Bonds

Triplet azide

matrix

phenyl

in both isolated

observation

nitrene

(51 and

is the predominant

PhN,.

but perhaps

of a previously

rearrangement.

N=

Ii

Related

product

of PhN e at 500°C

pyrolysis

more

spectrum

experiments

and

phenyl

is also

in photolysis

of

is the

the carbene

This

postulated

when

nitrene

surprising

when

(11 are decomposed.[l41

and

N,

Phenyl

at 77K.[131

of the nitrene

possiblity

(51.

to Carbon

is photodecomposed

observed

N,

N,

anions

verifies

precursors the

carbene-nitrene with

p-tolyl

and naphthyl

YNH NcN

azides

are also

decomposes material >1120K. such

reported.

to products of the

FCN

whose

reactor.[l51

is the exclusive

as F,C:NF

and F&N:NCF,

In a low pressure nature

depends

For example, product were

flow

system

largely

on the wall

with molybdenum

but possible

not detected.

CF,NJ

at

intermediates

5 Hydrogen treated 350K

chloride

with giving

yields

is

potassium highly

eliminated

when

t-butoxide

in

explosive

2H-azirine

CSl,

vinyl

which

can

l-azido-2-chloroethane

a low

pressure

azide.[161 be

is

flow

system

Pyrolysis

isolated

at

below

at

then

240K.

On

\ I HCYN

H&

the

other

hand,

hydrogen

simultaneously 710K

but

when

the

product

Conversion organic such

of

as

that

heat:

is

can

acetonitrile,

be

can

is

are

isomer

azides

at

by this

be

of

room an

Amberlite

also

directly

at

CSl. temperature

in

“azidising”

IR400

worked

method

lost

pyrolysed

by using

by treating

obtained

nitrogen an

to

facilitated

products

those

and

compound

halides

obtained The

among

initial

organic

solvents

azide.1171

chloride

the

with

sodium

up without

is

CH,(N,l,

has

been

polymer, applying

from

dichloromethane. A thermally first

time

generated (equation

nitrile 11,[181

ylide

(21

and methylnitrile

observed

ylide

for

MeCsN’-CH,-

C--N+sC-H

can or

be by

obtained

either

desilylating

Molybdenum

from

CH,N,

and

acetonitrile

Me(PhSlC:NCHZSiMe3.[19]

nitrido

azide

MoCl,(EtCNl, are

and

MoN(N,lCl[HB(3,5-Me,pyz)sl, positions

the

di-

a ligand,

Me,SiN =, and

with

compounds

containing

complexes, as

The

equivalent

. . . (11

photochemically

dimethyl-1-pyrazolylhydroborate treating

the

which by a 4:l

addition

been

3,5-

isolated

Na[HB(3,5-MeZpyzl,l.[201

and monoazides,

occupied

in

have

MoN(N,l,[HB(3,5-MeZpyzlSl

form

mixed

ratio

of

crystals the

di-

with and

monoazides. Fluoromethylamines.

Me,NCH,F,

Me,NCHF,

and

Me,NCF,,

have

been

by

6 quaternised and

to the appropriate

characterised a normal

and

structures

X-ray

Treatment gives and

coordinate for

that

both

Their

etc.[251 together

with

potassium planar

coordination

unit

and

alkyl

converts

can be obtained

by an alternative

Carbon to give

disulphide a salt,

to other free and

salts

This

acid.[321

structure

bonds

Reaction

exists

with

of acetimidoyl unknown

trithiocarbonate,

triazine

derivative

the

latter

atoms.

to esters, ester

by treating

which

and by HCl at 0°C

SCN-

between

and CN-.

with

MeSC(S).N:CMe.NH,,

A

conformations

interlinked 296.8

to the

H,N+:CMe.NH.CS,-

two different

molecules

MeC(:NHl(NHzl

can be converted

by S...H-N

and 337.0pm.[331 methyl

iodide

in addition

dithiocarbamate

and

gives to

the

C~l.[341

oxazoles

hexafluoroacetone

shows

S-methyl

salt

acetamidine,

dithiocarbamates

ester,

dimethyl

Substituted

with

to H,S.

in distance

pyramidal

sulphur

the phenyl

route

as the zwitterion,

planar

for the

trigonal

and

[271

of the

chlorodithioformate.[291

[30.311

solution

determination acid

ranging

the previously

at -15°C

hydroxides

in aqueous

for the carbamic hydrogen

reacts

synthetic

phenyl

acetone,

investigated

and three

[MeC(NH,121[SzCN:CMe.NH,I, by metal

decomposes

crystal

with

DME.

conformation

etc.,

with

of alkali

adduct

the potassium

for R = Me, Et, benzyl,

has

is C,,.[251

is in distorted

one nitrogen

halides

is 70.1":[241

water,

has been

is an E.E

are

PhN(CHO1,

to produce

for the dioxan

there

latter

in the presence

RSCS.NPh.CH:NPh

N,N'-diphenylformamidine

angle symmetry

acetonitrile,

potassium

disulphide by n.m.r.

The

analogue,

disulphide

decomposition

to one oxygen,

with

carbon

structure Here

salt.[281

S,CNCN

Reaction

thermal

an X-ray

the dihedral

with

silicon

and N(CH.51, groups

the molecular

solvated

M[S,CNPhCH:NPhl.

with

The oxygen

with

In

[Me,NCF31+

characterised

structure.[221

PhNHCH:PPh,

reacts

hydroxides,

for

[Me,NCHFzlI.

the phenyl

but here

and N(CHCl,l,

N,N'-diphenylformamidine. metal

reported

PhN(CHSl,,

(87.7").[231

structure

NACHO),

through

salts

spectroscopy.[Zll

was

and

and an X-ray

the planes

orthoganol

a similar

[Me,NCF,II

derivative

i.r. spectroscopy

almost

analysis

of N-bis(dichloromethyl)aniline

the thioformyl

shows

tetraalkylammonium

and vibrational

by n.m.r.

addition,

substituted

(111 are the product

obtained

and N,N-dialkylcyanoformamidines,

can be prepared

from

cyanogen

from HN:C(NR,)CN;

and a secondary

amine.[351

N/cbN I II

Me-C

(CF,),

C-Me

NH,

\,P

8-Azaguanine

(12. LH,) and 8-azahypoxanthine

(13, L'H,) form

compounds in aqueous solutions at varying pH’s

methylmercury

(12)

(13)

formulated as MeHgLH, [(MeHg),LI.H,O, and (MeHg),L'.[361

An X-ray

structure for the latter shows bonding with the Nl and N9 atoms: in [Zn(H20)(L'H),I the N9 position is also the coordination site. 5.1.3

Bonds to Oxygen

Hydrolysis of a series of hydroxylamine sulphonates,

i.e.

(MeSO,),NOH, (MeSO,),NOMe, MeSOzNH.OSOzMe, MeSOz.NMe.OSOzMe

and

(MeSO,),N.OSO,Me, has been investigated over the complete pH range tOH(MeSOZ),NOH B

(MeSO,),NO-

--3

MeSO,NO + MeSO,-

-Hz0 20"I MeSO,- + NO,- + Hz0

. . . (2)

and for the first compound, the steps outlined in equation (2) are followed.[371 A reexamination of the of the chemistry of tetramethylammonium

8 superoxide compound

shows with

suggested with

reported

acetonitrile.

the acetamide preparation

the

adduct, also

dimer

to be a peroxide :NH. which

MeC(O0)

it be replaced

some Me,NOH by the

on hydrolysis

and Me,NOOH,

reaction

gives

The original

[MeC(O)-(OH)NH,I.[381

produces

addition

and

of potassium

it is superoxide

Me4NOH.H,0.

Reduction 100°C

of both

N,O and NO to nitrogen

in the presence

following

being

important +

2NO

+

CO

-----i

N,O

N,O

+

CO

---t

N,

2N0

+ 2C0 ----iN, + 2~0,

of i.r.

linear

and

the

. . . (3) . . . (4)

. . . (5)

nitrosyls,

x = 1 and

data

for

bent

NO group

one

at

with

c&z

binary

for

addition,

monoxide

investigated

steps.[391

of iron and nitric

the

characterised

by carbon been

t CO,

Cocondensation isolation

has

of Rh,(CO),Cl,

oxide

has

Fe(NO),

2 by Mossbauer

n = 4 point with

to

led

for

to

matrix

X = 1-4, In

spectroscopy.[401

the

presence

of

pseudo-tetrahedral

three

symmetry

about

iron. N-nitrosohydroxylamine-N-sulphate kinetic

study

hydrogen with

of

the

sulphite

hydroxylamine

over and

pH range

the

substituted

MeNHOMe. requires

NO to

HNO.[421

hydroxylamine reduction reaction cannot

Trace

reaction

involves

but with

product

observed

in a

NO with

sulphite

and

Reduction

4-10.[411

hydroxylamines,

abstraction amounts

abstraction

is inhibited

the

of dissolved

the

NH,OMe and form

is

reaction

of

an N-bound

of oxygen

N,N-dialkyl

catalyse

since

atom. a reactive

the

This anion

be formed.[431

N/“==Hg_Hg_=Oo~Nng_N/o*=:Ag lo.”

-w

“0

/’

Ao=-

NO

hydrogen

hydroxylamines

at the o-carbon

by 0-methylation

of

MeNHOH, by

9

The mercury(I) nitrite structure contains the almost planar molecular unit (Ml

with mercury distances to mercury and oxygen of

252.0 and 224.41257.7pm AgzLi(NO,f,

respectively.[44]

In the ternary

the basic unit ffif is also almost planar and the short

Ag. . . N contact (224.lpm) suggests some degree of covalent interaction. Some insight into the.mechanism of the reduction of NO, to ammonia has been gained by an investigation of the electrochemical oxidation of [(terpyl(bipy)M(NH,)12' and reduction of [(terpy)(bipylM(NO,)l+

(M = Ru or 0~1.1451

The critical step is

interconversion to the nitrosyi form which can undergo a series of one electron reductions. The

complex

reaction

of sodium

nitrite

and

sulphur

in DMF,

DMSO

and HMPA has been investigated by the whole range of spectroscopic methods supplemented by gas analysis and chromatography.[461 Inter alia, the reaction leads to nitrous and nitric oxides, thiosulphate, polysulphide, polythionates and nitrate with the first step being the formation of perthionitrates, NaS,NO,.

These

can then either decompose to N,O and thiosulphate or react with nitrite yielding nitrate and perthionitrite, NaS,NO.

Colour

changes during the reaction from blue-green to orange-red are due to the formation of blue S,- and red ONSS-. A new synthetic route to NzO, involves reaction of nitryl fluoride and lithium nitrate, the product is very pure and detailed Raman spectra are reported.[471 Catalytic reduction of nitrate to ammonia has been observed for the first time using a modified glassy carbon electrode

in water in

the presence of [Bu4Nl,[Mo,Fe,S,ISPh1,1.[481 Structures of three basic mercury(I) nitrates, all hydrolysis products of mercury(I) nitrate dihydrate. i.e. [(Hg2)20(N0,11N03.f(Hg,),(OH)4(N0,)zlfNO=)~ and [Hg,fOHglzl(NO,fz, show the HNG, mercurioxonium ion as a common feature of all three structures.[491 In the first it is an infinite chain species with the solvate nitric acid molecule hydrogen bonded to one of

the nitrate ions.

The second compound contains a finite four oxonium chain while the last contains an infinite folded layer with both Hg(I) and Hg(II1 atoms. Three bidentate nitrate groups and four water molecules give the europium atom in [Eu(N0,1,(H,0141.H~0 ten-fold, bidapped square

10 ant iprismatic, coordinated

5.1

4

Bonds

nitrate

study

[Me,NClHIX

addition

2501255,

for Me,NCl

and the

reorganisation

(N-B

between

at -50°C

IX = CF,SO,.

compounds.[511

for Me,NCl.BCl,

dioxide

to the oxygen

are 2521263,

are now available

salts

trihalide

groups

atoms

of

and 2471258pm.

to Halogens

1.r. spectra prepared

Distances

coordination.[501

the

167pml.

to both

and BCI,

In addition

Me,NCl.BF,

leads

SO,F

According

and boron

there

is an X-ray

to n.m.r.

and Me,NCl.BCl,

BF,Cl

recently

and BFCl,

evidence,

in liquid

adducts

sulphur

of dimethyl-

chloramine.[521 Tertiary R,PCl,

are oxidised

by nitrogen

trichloride

(R = Me, Et, Bu or Ph) with

phosphines

elimination

of nitrogen.

Phosphorus

trichloride

chloramine.

PCl,

is similarly

gives

a mixture

oxidised

to PCl,

of trimeric

to

but with

and tetrameric

cyclo-

chlorophosphazenes.[531

5.1.5

Bonds

Although

compounds

in Chapters tricyclic compound

3-6,

Non-metals containing

a number

product when

chloride: and

to Other

(16)

such bonds

are noted

is obtained

An

in place

(171 and PhB(NHMe) 2 are

the product

are discussed

here.

is stabilised

in detail

interesting

of the expected

refluxed

in carbon

by coordination

tetra-

between

boron.[541

Ph MeiN,

d,NiMe CIMe,SiN/S'NSiMe,Cl

Me-B

B-Me

?

I

N/'\N

SiMe, 'S'

I

I Me,Si

1

Me&i

/

\

CC)

SiMe, 'S'

Two

groups[55.561

containing outlined

have

reported

a silicon-nitrogen in equations

(61 and

the preparation

double

bond

using

(7).

The t-butyl

of products the reactions substituent

sulphur

11 Buti,SiCIN,

+ NaSiBu',

Pr',SiCl.NLiR

---* NaCl

-----t LiCl

+ N, + Bu",Si=N-SiBu*,

. ..(61

. . . (71

+ Pr',Si=N-R

(R = 2.4.6-C,H,But31

compound and

has

reacts

bonding

silicon-nitrogen

with

THF

is exclusively

188.81186.6pm second

decomposition

was

independent

isolated

at 97-99°C.

A theoretical

H=Si:NH.

to an angle

low barrier

effects

silicon

of 126.6"

atom

melting

at b 60.3

of the model

groups

will

169Spm

(Si-0

also

The without implies

compound,

at the nitrogen

to linearisation.[571

of attached

and

in which

present).

crystals

resonance

treatment

(6.0 kcal.molll)

negativity

of 156.8 compound

molecules

as orange

its zgSi

unsaturation. points

distances

via the unsaturated

in the two

compound

bond

to give a 1:l addition

atom

but a

Eletroaffect

the nitrogen

angle. Continuing structure to those place Si-N

on silylamines

in related

in the solid distances

distance Both been

work

for SiH&l(NMe,l

mono-

a monomeric,

gas phase

(Si-N

168.9pml

Dimerisation

however

a centrosymmetric

to 181.4/205.4pm,

similar takes

structure

elongation

with

of the Si-Cl

observed.

by treating

hexane-dichloromethane

Pr'

to give

and diprotonated

isolated

parameters

compounds.[581 state

increased

is also

has shown

with

cyclosilazanes

(Ml

(Pr',SiNButl 2 with

solution.I591

Pr'

X-ray

Pr'

and

(19) have

aluminium quality

chloride crystals

in

of

Pr'

'Si'

But_/

’

N’/

Bu”

AlCl,-

[O(AICl~l,lZ-

'Si/ 'H / \ Pi-' Pr'

/\ Pr'

(191 could

be obtained

to

from

179.2pm

the

Trisulphonylamines, of aminostannanes

showing

174.7pm

an

increase

in the starting

N(O,SRl,(O,SR'l.

Me,SnN(S02R12

In the sulphur-nitrogen

field,

Pr'

in the Si-N

separation

material.

can be prepared

by cleavage

with

a sulphonyl

chloride.[601

the

interesting

ring expansion

in

12 equation

(8) can be achieved

by treatment

with

either

(Me,Si),NSN

. . (81

E = Me,NC,

Et,NC

Pr,NC

or R,P

The

or Me,SiNS0.[611 product S-S

an eight

bond

latter

membered

A \

Bonds

Weak

potassium

and

small

sodium and

Cs may

addition

cesium

have

1.r. band ammonia-metal

behaving

as weak

suggest

A tetrameric +3 and

yields

as a minor

(20) with

a trans-annular

\

S-r=-N

1 N-S-N

S-Cl

9

compounds been

titanium

identified

lithium,

sodium,

by matrix

isolation

are consistent

with

calculations

charge

transfer,

both

lithium

Lewis

acids:

role

and

interactions

of

and for K

reversal.

containing

is obtained

ammonia

with

increased

acid-base

compound

states

in liquid

with

shifts

possible

+4 oxidation

borohydride

N-

to Metals

1:l ammonia

methods.[621 very

also

(243.2pm).

Me,N-C

5.1.6

reagent

ring compound

the metal

by reducing

is formulated

in both

TiBr,

the

with

as

[NH,.NH412[Ti4Br,(NH,),,1.[631 Recently compound

are

compounds ammonia

reported similar

were under

structures to those

obtained

for Rb,[La(NH,),I for K,[Cr(OHl,I

by treating

pressure.[641

The mixed

and CsLi,(NH,),.

obtained

infinite

ILi(NH214,,-I

lie at the centre

of a distorted

metals

cesium-lithium

containing atoms

and K,CdCl,;

the appropriate

CsLi(NH,),

twisted

and the neodymium

similarly,

have

chains

tetrahedron

the with

compounds structures

where

the

lithium

of nitrogen

13 atoms.1651 New tungsten

nitrene

complexes, have

WBr,(NCBr,).NCBr,[671

WC16 with BrCN. to

an

In both

a triple

cases

bond.

[WX,(NRlI-

the Both

species

halide. from

iminoborane,

on

An osmium

gives

the

been

W-N bond

distance,

compounds

reaction

can

with is

as

the

and

former

from

from air

bonding

(Ti-N

and

corresponds

to

anionic

phosphonium

results

oxidised

WBr,

170pm.

converted

an appropriate

a white.

by treating

latter ca.

be

OsF,(NCl),

reaction

material

the

and

Crystallisation

pure

(a)[661

reported,

ButB:NBut,

nitrene.

an OsF,/Me,SiNCO

trifluoride.[681

including

when the

with

mixture

chlorine

anhydrous

hydrogen

sensitive

solid

fluoride

melting

at

170-4°C. Titanium-nitrogen ligand

double

attachement

is

found With

CpTiClz(NPPh,).[69] ligand. Side

is

side

on bonded

on bonding

is

CpTiC1,(NPhNHz) [MePh,Pl’

cation

or

have

been

nitrido

WBr6 or

TaI,

350-400°C;

184.5, This

Ta-N

gives The

with

complexes = Ph,P, discussed.

of

metal

etc.1

the

with

other

end

hand,

of

hydraxide

the ligand relation

A gold-nitrogen

and

on

ca.

the 200pm.

complexes,

by treating from

metal

symmetry the

to

i.r.

for

the or

in and

the

1741 n.m.r.

containing

of

NbBr,,

as

bridge

(Nb-N

molecules.[721

MoCl,,

+4 oxidation

M[N(CNl,I,

cluster

ammonolysis

ReCls

interactions and

either

nitrido

WCl,,

in

with

formulated

linear of

[Mo,NClsl-

dichloromethane.[711

complexes,

D4h point

[731 in

the

result

ammonolysis

M[N(CN),I,L, py.

complexes

with

(NH41zMC1,, nature

with and

separations

isolated

a symmetrical

184.7pml

contrasts

in

MoCl S in

with

bridged at

182pm)

on the

Ti-N

[Mo,NC~,I’-

[MoNC141-

contain

ca.

CpTiClz(NCBu”Bukl

CpTiCl,(NHNMe,l.[701

Related [M,NX,,13-,

two

observed

complexes,

as

both

CpTiClz(NNPhl

with

also

and

Two*lJ-nitrido [MoNC1,IZ-

in

which

state.

dicyanamide (M = Pd or data four

Pt

has

been

metal

and

and

L

14

twelve

nitrogen

gold(I)

iodide

atoms

form

shorter

a rhombus

than

bidentate the Au4

atoms

diphenyl

PHOSPHORUS Phosphorus, initio

symmetry

Further

ab

36 k.cal

P,

strength

mole'

four

(mean 285pm)

is completed

alternately

and

mol-'

it may

above

gold

is

by four and below

is stronger

than

stable

than

that

that

(23) which

inert

in HP=PH and HP=NH

between

the

isomeric

results

both

when

be possible

studies

compared

Fe,(CO),

point

with

and

to a

values

respectively.I781

between

of X bond two phosphorus (22 k.cal

is calculated H,PP

to

for P,, cycle-P,Hs

two silicons

side

above

has an energy

as a measure

the bond

a D,,

mol.'

gas matrix.1761

Theoretical

trans-HP=PH

of a PEP unit,

latter

are available

for HN=NH

the diphosphene

of P, within

lies 6 k.cal

therefore

can be taken show

P,

to the

to rotation

to rotation

and the data

more

although

butane.[771

barrier

Coordination

that

calculations

and 47 k.cal

cluster

between

The

and Phosphides

in a low temperature

initio

mol.'

barrier

mol-'

ligands

decomposition

tetraphospha-bicycle

Further

separation

structure

on the trimerisation

indicate

of 13 k.cal cyclic

atoms

The

Polyphosphines

Pz fragments,

detect

63.5

the atom

triazenido

calculations

pathway

barrier

The

from a reaction ammonia.[751

ring.

5.2.1

three

where

isolated in liquid

in the metal.

5.2

Ab

has been

and Na(PhN,Ph)

mol-').

to be ca. 27 k.cal

form. and end-on, reacts

occurs

in the

with

(OC),CrPBr,.[791 Cis-trans and

reaction

mixture

(OC),Fe

of

isomerisation with (s),

oxygen (25) and

of But,C,H,P=PC,HzBu", at 80°C

over

(=).[801

three

has been

days

Magnesium

shown

reviewed

to give

dehalogenation

Fe CO),

(24)

a of

15

(menthyl)PBr,M(CO),, both and

substituted

diphosphenes,

phosphinidines

two chromium character

for M = Cr or W,

were

(P-P 204.0pm)

determined

formation.

Complexes

containing

the 0 =-bonded

are products where Mono-

related

PhP=PPh

can be obtained

complex

and PhP(SiMe,)z

observed with

while

[P(SiMe,)Butl,

for the first

an excess

the phosphorus amount

intermediates.

of the double

out

P(SiMe,),

for both

with

linked

Bu' ,C,HzPC1,

converts (2J).[851

compounds,

Complexes

i.e.

chloride

can be

diphosphene

The products

gives

the

material.

by a carbonyl

were

has been

was (27).

bridge,

X-ray

(28). Treatment

treated

in which

and a small

structures

were

of Cp'Mn(CO)(NO)-

the diphosphenyl

1841. while

Cp"M(CO),-P=P-C,HzBut,,

nickel

Cp"Fe(CO)zP=PC6H,Bu",

complex

are

containing

the original

of a coordinated

compounds.

Cp'Mn(CO)(NO)P=P-C,H2But,,

or Ph, with

as starting

bond

of the diphosphene

carried

from

time when

are

diphosphene

by treating

Ni[R,PCH,CH,PR,I[P,Bu',l

of Fez(C0),.[831 atoms

of the

and Ni[R,PCH,CH,PRzl[P(SiMe,),lz

stable

using

for the

bond

of the x-bond

and di-substituted

low temperature

Cleavage

double

silylated

obtained

R = Et, Hex"

NiC1[R,PCH,CH,PRz][P(SiMe,),l

prepared

Structures

showing

and non-involvement

in complex

NiCl,[R,PCH&H,PR,I,

containing

(OC),M.(menthyl)P=P(menthyl).M(CO),,

diphosphene

LiP(SiMe,),.[821

to complexes

(menthyl)P[M(CO),1,.[811

compounds

(Me,Si)P=P(SiMe,)

leads

an excess

complex, of nickel

carbonyl

for M = Fe or Ru to the adducts

16

Cp'Fe(CO),P=P-CeH,Bu&3

Cp*Fe(CO),-P

I Fe(CO),

(27)

(28)

Cp-M(CO),-P=P-C,HzBu",

I Ni(CO),

The

general

reactivity

Pz[C,HzBu”,lz.

towards

investigated.1861

of two diphosphenes. electrophiles

With

hydrogen

(Me,Si),C-PH-PCl-C(SiMe,), amount

used,

while

with

HBF,.Et,O,

equivalent

of hydrogen

[RP=PRAgl'

and

and

with

methyllithium.

Electrochemical = (Me,Si),C stable arsenic

to be

similar

reduction

species

can also with

with

leads

in naphthalene

only

occurs

one

from

then

gives BuLi

anions are

reaction

on treatment

with

spectroscopy;

be obtained.[871

sodium

cleavage

using

result

occur

to radical

by e.s.r.

is

is produced

[871 which

on the

and di-cations,

methanol

reactions

and C,H,Bu",

investigated

[(Me,Si),CI,P,

[RP-PRMel-

Quenching

[87.881

Both mono

(R = C,H,BU"~).

the anion

RHP-PMeR:

even when

chloride.

[AgRP=PRAg]"'

Ag[SO,CF,I

diphosphine

analogue

gives

depending

P=P bond

hand.

and

has been

the former

the product

On the other

the tri-t-butylphenyl

with

chloride,

and PHCl[C(SiMe,),l,

[PH,(C(SiMe,),)l[BF41. with

P,[C(SiMe3)312

and nucleophiles

the and Bu"Li.

[R,P,l--

for R

sufficiently the related

Treatment apparently

of gives

the same

species.[881 [2+1] Cycloadditions phenyl

and anisyl

phenylazide

and

between

diphosphenes.

sulphur

the chromium

carbonyl

[l?P=PRJ[Cr(CO),I,

lead to the heterocycles

and

complexes

of

respectively

(30) and

17 (2).

31P

[891

n.m.r.

Ph

shifts

for

a

(OC),Cr

range

of

’

\

Ph

\/

6 metal

P -_

P /

anisyl

‘P-P’ (OC),Cr’

Group

fOC),Cr’

\

N

/

(°C)5Cr

’

anisyl

S

I

Ph

(30)

(31)

complexes

with

have

interpreted

been

solution. Addition the

diphosphenes. in

of

aluminium

their

and

phospha-allenes

structures

chloride

product

starting

leads

material For

to

a

in

dichloromethane

tetrachloroaluminate

chloromethylation

[911

of

[901

triphosphenium

(34-j.

phospha-ethenes terms

the

(33). to

second

a

(32)

but

gives

further

solution initially

reaction

with

the

1.2-diphosphoniodiphosphirane

stage

of

the

reaction

to

dication proceed,

CH,Cl +

of a

it

2+

I

1 Ph,P

Ph,P

P&Z

(32)

/p\

PR,

(33)

Ph,P

/p

(34)

is

essential

that

one

of

the

phosphorus

atoms

carries

an

amino-

18

substituent

and

piperidino

and

available A new 1982

R,

for the review

KPH,

at room

400K,

same

and

with

and RbPH, with

limits

work

P-P bond chlorides

of transition

metals

a NaCl

formation

high

only

are treated

can be obtained

while

with

with

but

Two

Bu'-C 362 H PCl,,

I96,971

Me,M,-Me,M',

and

the

type

when

and M"

to give

Me,PAsMe,

exchange

report

is a Group

for example,

mixtures.

the

in liquid

forms

salt

form.

is

Both between

Between

110

the

structure.

phosphonous

or phosphinous

homogeneous

for R = Bu",

the products

since

lithium

reducing Good

Hex",

agent yields

of

Ph or mesityl

are either

) or Bu'~C,H,P=PC,H,BU~,,

depending

either

systems

be

where

on the

of Me,P,

(equilibrium

0.26)

solution,

and Me.Sb,-Me,As, in the Me,P,-Me,Sb,

in 6 days

at 25°C.

exchanged

and crystals

Mixtures of

by fractional

Me

(35)

5

and

constant

or in benzene

Me,Sb,-Me,Bi,

was detectable

isolated

in the

M and M' are Group

Mixtures

liquids

with

however

(35, M = As and Sb) also could

rapidly

as neat

occurs

No exchange

thermochromic.

systems,

on exchange

6 element.

exchange

similarly

and Me,P,-Me,Bi,

the results

M,M,-Me,M",

Me,As,,

and

is

stoichiometry.

papers

elements

or

complexes

phosphine.[941

temperature

the mild,

from RzPC1

Bu" ,C,H,PCl-PCl(C,H,Bu", reaction

NMe,

surveyed.[931

crystalline

the CsCl

is promoted

been

to cesium

MPH,

and evolves

different

type

shows

lithium

to give

temperature three

has also

from

area

metal

1.3.1' .3'-tetraethyl-bis(2.2'-imidazolidene).[951 RRP,

=

structure

X-ray

in the polyphosphine

the chemistry

phosphine

have

CsPH,

An

R

latter.

of alkali

react

unstable

Bu"(piperidino),.

=

for

isolated

been

P, P,, P, and P, units

Solutions ammonia

have

summarises

review,[92]

containing

and

compounds

of

(361. which

crystallisation.

.Me

(36)

is

19

In systems

involving

Te, exchange

with

corresponding

Treatment leads

Me,M,.

mixed

Raman

n.m.r.,

Croup

where

products

and mass

where

(37) with

salt

which

were

gave

the

characterised

the diphosphate

a dichlorophosphine.

(38) which

by

can be reduced

R2PClz,

with

Bu,P

(El.1981

P-

P-P

P-Cl 1 RZ

\

/ R2

R'

(37)

\ R'

(39)

Products,

including

(R=Bu" &,H,)

RHP-PHR.

are obtained

temperature

with

ring,

RHP-PClR,

when

K[CpMo(COl,l;

one of the products

however, a P,Mo

M2 = S, Se or

M = P, As, Sb or Bi,

Me,M-M*Me,

of the phosphete

R2

MeZMzZ

spectrometry.

to the phosphetium

to give

6 methyls,

which

shows

RP=PR

But ,C,H,PCl, at higher

is a novel

slight

and RP[Mo(COl,Cpl,,

reacts

rection complex

multiple

bond

at room

temperatures, (401 containing

character

in the P-P

in THF or potassium

naphthalide

system.t991 Bond

cleavage

in the three has been

by either

membered

studied.

the dipotassium

heterocycles

salt,

Me,SiCl.[lOOl

asymmetric observed above

-78°C

cleavage metallation

compound -78°C

to KPHBu*,

with

and

which

salt

but with

P-N

compound

gives

can be converted

and P-B

(431 there

systems

rearranges

P-P bond

KBu"P.CMe,.PBu'K

which

cleavage

These are

fully

to the is also

decomposes

is preferential

KBu"P.PBu'.NHPr'.[lOl] P-C,

(431

(Me,Si)ButP.B(NPr',1.PBu*(SiMe3) the potassium

KBu*P.PBu'.BHNPr',.

(4J), giving

to give

(42)

the first

KBu'P.B(NPri,l.PButK.

Above

analogue with

(411,

At low temperatures,

to the trimethylsilyl with

potassium

P-N

differences discussed.

in

20 co

CP

But-P \ I,

\/ MO /co

BuL.C 3-z H -P '

B-NPr',

But-P H-Bu t 3 6L'

'P-C

Bu'-P \ I Bu"-P

(43)

(42)

A new equation

three

NPr' /

membered

(91. where

P,C heterocycle

R = 2-Bu"C,H,,

(441

is formed

2,4-Bu",C,H,,

as shown

2-Me&H4

in

or

mesity1.[1021

Bu*P\ Kz[Bu"P.PButJ

+ RN=CCl,

--)

I,C=NR

+ 2Kc1

. ..(9)

Bu'P (441

In addition with

sodium

to other in liquid

H,N.PH.PH.PH.NH,, liquid n.m.r. The

ammonia

spectroscopy

obtained

and

subsequently

reacts

further

tetraphosphines The

of white

phosphorus

the diaminotriphosphine.

the compound

its structure

is stable

can be

only

investigated

in by 31P

at -6S"C.[1031 triphosphines,

when

the reaction

gives

and although solution,

substituted

are

products, ammonia

either treated

with

with

RPCl,

where

is metallated

Me,MC1.[1041

where

(Bu'Pl,P.PClR.

cyclotriphosphine

(Bu"P),PMMe,

(Bu'Pl,,,,

The

M = Si or Sn,

with

R = Cl or Bu" to give each

containing

(451 on treatment

potassium

tin compound the

a P, ring

in a sealed

system.

tube

at ca.

21 200°C

with

sulphur

respectively compound major

or

(46, (p8,

47

X = Se)

product

in

selenium and 48,

the

in with

1:3,

was detected 1:6

ratio

1:5

and

X = S or

I:6

ratios

by n.m.r.

experiments

gives Although

Se).[1051 spectroscopy, was,

in

fact,

the (47.

X =

Se).

Me

Me

P-l-P

(46)

145)

Me

Me

(48)

(47) Substituted reaction or

Ru but

(50,

cyclotriphosphines

between

tetaphosphines

n = Ru)

A number phosphine

of

has

been

papers

mixtures

(9)

(mesityl)PCl, (50)

and are

determined [107-1111

by 31P n.m.r.

are

the

by-products by

deal

major

products

Cp’M(CO),P(SiMes),, X-ray

and

for the

structure

diffraction.[l061

with

investigations

selective

population

of M

of transfer

= Fe of

22 mesityl

mesityl \

P -.P

,+,

\A

Cp*(COlzM-P(p)Pn(CO),Cp-

mesityl 7 M(CO),Cp"

Aesityl

(50-j

(49-j

experiments.

For example,

isomeric,P(PH,), P,H,

and

have

their

been

n.m.r.

containing

lo-151

show

three

forms

P,He

is formed

d-.

identified

in mixtures

parameters

defined.[l071

obtained

by thermolysis

P,H,

of n-P-H,

and the

iso-form

not as a six-membered

phosphino-cyclopentaphosphine stoichiometry

l- and meso-forms

there

P(PHz)(P,H,),,

(51).

is evidence

and the

containing

26-48%

Mixtures of P,H,

similarly

P(PHzlz(P,Hs).[1081

species

[lo91 while

for three

two of P(PH,),(P,H,)

HzP

ring

of n-P,H,

but as

distinct

together

the

for the P,H,

with

forms

of

the highly

\ -PH /p

Hp\PH

;,,

symmetrical

2.3-diphosphinotetraphosphine,

In the P,H,

system,

A 3:l molar

ratio

iso-triphosphine

ClP[P(SiMe,)Me], symmetry

isomeric

form

H,P.P(PH,).P(PH,l.P,H,.

phosphine,

the

one

with

as

has now been

of MeP(SiMe,l,

and PCl,

PIP(SiMes)Mel,,

distances

identified.11111

reacts

at -78°C

via Cl,P.P(SiMe,lHe

intermediates.[1121

P-P and P-Si

H,P.P(PH,).P(PH,l.[llOl

of 2,3-diphosphinopenta-

The product of respectively

to give

and

has almost 220.1

and

225.2pm. Alkyl

lithiums

P,Bu" ,SiMe, loss

and

(RLi)

of one Me,Si

P,(SiMe,),. cleavage

react

group;

P,Bu"(SiMe,),

to give

with

the cycle-tetraphosphines,

trans-P4Bu",(SiMe,),. but with

to give monolithiation

the related

and cis-PaBut,(SiMe,),,

n-tetraphosphides,

with

tetraphosphines, there

LiP,Bu',_,(SiMe,),R

is P-P (n =

C,

23

Even

2-4).[1131 compounds phosphines, to room

e.g.

converted

voltametry

pentamers

are usually

pulse

conversion

and on warming

P,(SiMe,),

P(SiMe,l, can be

of RPClz

complex,

unit

Currently, An X-ray

complexes

five-membered electron

and

prepared

melting

phosphorus

of other

Pq with

in xylene

the

obtained

between

at

14O"C.[1161

contains

are

three

(521 containing

from a reaction

at 15O"C,

P, as a 6n

between

as air stable,

white

sublimable

at 27O"C.[1171 oxides

air oxidation

retains

(531-(561

of PsBue4

one of its triangular to give

A new structural

can be

and P,Bu",.[ll6] P, faces

the new hexaphosphine

type

for the P,R,

composition when

of the cyclotriphosphine

MePCl,;

equimolar

of the

(591 react

reactants

with

when

it

derivative

results

(~1.11201

known.

parallel

(581, a bis(cyclotriphosphino)phosphosphine,

quantities

can be

stabilised

P 6 and As, units

species

to have

Lip,

LiPH,.

containing

cyclic

A second

to give mixtures

all considered

the new compound

to Cp,Zr[P(SiMe,),],

(57_).[1191

amounts

from a reaction

cyclopolyphosphine

by controlled

and

structures.[llSl

phosphorus

[Cp"Fe(COl,l,

pure

to cyclophosphines,

in diglyme

anions,

by treating

containing

has been

crystals, first

P&H,-

isolated

shows

rings.

donor

phosphorus

by sodium

monocyclic

and white

structure

Small

Cp'Cr(Ps)CrCp',

has been

[Cp‘(COlnCrl,

provide

obtained.

P,CH-,

state

polarography

for R = But or 2-BrC,H4

is cleaved

in a pure

cycle-P5

also

stabilised

A chromium

White

In this way,

of tetramers

of the PT-,

obtained

adds

the secondary

such as LiP(SiMe,),.

and differential

phosphorus

of salts

The

phosphines

for R = Ph or 4-BrCsHs.t1141

sizes

mesomerically

green

silyl

are eliminated.

formation

White

solution, to give

LiPtP(SiMe,)R]tP(SiMe,)P(SiMe,),l.

on the electrochemical

showing

in THF

into Lisp,.

Cyclic

ring

low temperatures

via a 1,3-LilSiMe 3 shift

temperature

or RP(SiMe,l,

data

at

rearrange

two mols

lead to the chlorotetraphosphine

24

BU’, \

P-

Ft P-Bu’

P -

\

\/ p\P

/P-Bur

Fe

Bu*

Bu” \

t!

P-P-

\

\/

But

But_

BU”

0

Bu”

,“\

tip/

Bu” Bu’_P

\p/p-p

/

‘P

-‘“‘

‘PA

1 \

\

‘,t

’

P BG’

(56)

p\

Cp,Zr -

1

I P’

P(Me&i

But-P P-PtSiMe,),

\ I

But-P

/’

/ -

,9,‘\P_B,k

),P’ (57)

(58)

P-Bu” I

25

But-P \ I/ Bu'-P

P-SnMe,

(59)

Germanium

and

(60)

tin derivatives

(61, M = Ce or Snl either

Ph,CeCl

crystal The

structure

structures

lithium

temperature

(61, M = Sil N.m.r.,

when

Li,P,,

214.7

obtained

from

with

compounds.

a high

crystallises

is surrounded and 217.6pm

reacts

cage

i.r. and single

for all three

of the elements,

the cage

224.9,

are available

salt,

reaction

distances,

when

or Ph,SnC1.[1211

X-ray

related

result

of the P, nortricyclen

in a new

by 12 lithium for basal,

ions:

the P-P

basal-bridge

Pr' \ Ph,M-P'P'P-MPh / P-Mph,

3 p\P /

Pr'

\

'PA '-c,"

P"\pr'

\

I

I/

PAPAP (61)

and

bridgehead

distances

respectively,

heptaphosphoranortricyclen M 7 se systems the mixed

has been

[P,_,As,13-

stoichiometric are

observed

the

series

mixture

[P,_,As,19-

constitution mixture magnesium

cage.[1221

investigated species

has been

obtained

when

meta1.[1241

Valence

with

solution

of the

tautomerism

by a 3'P n.m.r.

(x-31 obtained

typical

study

by heating

and assigned

in

of a

Six

of Rb. P and As to 9OOK.[1231

in ethylenediamine

A new octaphosphine,

are however

signals

to species

in

x = O-5.

PePi-"., (621. with

a homonorbornene

isolated

by thermolysis

mixtures

of Pr'PCl 2 and PCI,

For a phosphorus(III1

of the product are treated

compound,

PeButs

with is

26 surprisingly

stable

(63) by hydrogen

but

it can be converted peracetic

peroxide,

acid

to an octa-oxide or cumene

hydro-

Bu"

\

But

(63)

R\P/Plp / P

/p’R

I 1

'\R

p\P/p (64-j

peroxide.[lZSI thermolysis ZOO-220°C ation

Pure

and

the

related

isomeric

type

A central

and

with

shown

essential

structural

have

by reaction

structure

(64).

show

they

at

by dehalogenComplete

are based

on a

in two configurational

the realgar.

obtained

been

of white

to C,,

of Hittorf's

isolated,

phosphorus

(66) deduced -

THF.[129] from

The

phosphorus.

sodium

detailed

full P,, the

Two P,,=-

by disproportionasodium

in the presence

P 193)- anions

in

of Pr'PCIZ

and contains

and the solvated

with

is found

a mixture

symmetry

Li,P1,.8THF

solution,[l281

in boiling

structure

in THF solution.[l271

element

in THF

cradle

by dehalogenating

in (65) has close

recently

of Li,HP,

with

magnesium

structure

18-crown-6

can be prepared

by

mixtures

and PC1,.[1261

spectra

structure

P, unit

previously

tion

can be obtained

forms.

P12Pri4. PCl,

t-butyl

of Bu'PC12

of the 31P n.m.r.

deltacyclane

of PsEt,,

P,Et4 -Pa or P,Et,-P,Et,-P,Et,

of a 1:2 mixture

analysis

salts

samples

of either

with

two-dimensional

n.m.r.

salt of

27

pp
/

p\\

I

p

APL.

P-2-P

P

Kpr’

I \

/ \,/pI\,Ip\,,,

PLP

/

(65)

spectroscopy

can be obtained

nucleophilic

cleavage reaction

potassium, Li,P,&

with

in P,,2of Na3P2, metallated

with

either

of Li,P-, with

LiPH,.t1301

formation

in a number

of Ps with

from PTJ-.

alkyl

bromides

compounds.

white

The compounds

Finally or Me,SiCl

such as NaP1,Me,,

of ways

including

LiPH 2 or metallic phosphorus,

and

are possibly

in this leads

\/

/ln\X

w

/ln\X,lnl

reaction

intermediates

section,

treatment

to partially

NaPz1Et2.

NaPZIPri2

Nap,, (SiMe,),.[l311

\InlX\In~X\Inl /\ x /\ x x x

sodium

/\

x

\/

x

and

or of

28 Strings

of edge

and

(67_, X = P or As), phases

Sr,In,Ps

elements Figure by

vertex

are

found

1. contains

(SnPSnl

bridges

membered

obtained

The Ba,Sn,P,

infinite groups

Sn,P,

InP, or InAs&

in the structures

and Ca,In,As,,

to 250K.11321

linking

sharing

a series Among

of the new

by heating structure

of

units

(SnP,Sn)

Zintl

the

shown

(SnzP,l"-

via one double

to give

rings.[1331

chains

tetrahedra

in formed

and two single

of alternating

four

new polyphosphides

and eight

obtained

during

sn OP 0

-

Figure

1.

the period

Structure

of Ba,SnzPn

Z. Anorg.

Allg.

under

review

ZrFe,Si,

structure),[l351

SrPt,P,,

SrPtaAs,.

phosphorus

atoms

Chem..

are:

CaCu,P* with

chains

the vacancies1,[137] structurel.[l381

Bonds

isolated Hex".

to Group

reactions

t-butyl

(mesityl),l

P-B

with

borine than

planar (ca.

sharing

of calcium

copper

and

tetrahedra

and HfCu,P,

P-B double

of RPHB(mesityl1,.

and

are monomers

geometry 183pml

(681 on the other monomer,

bonds

where

about

suggesting

X-ray

single

phosphorus substantial

of the substituted

hand

produces

even

though

or

[Li(Et,Ol,RPB-

[Li(l2-crown-4),1-

from both

has been

R = Ph, mesityl

The compounds,

or Hex"

Dehydrohalogenation

a n-bonded

type

structure

and ZrCuzP,

containing

for R = mesityl

separations

character.

of edge

lithium.[l391

I(mesityllPB(mesityllzl studies

type

(with a

3 Elements

of compounds

from

with

from

structurel,[l351

and BaPt,P,(pyrite

(CaA1,SiZ

A series

ZrNi,P,

(CeA1,Caz

(rutile

occupying

5.2.2

by permission

532(19861731.

TiMnZPIZ,[1341

ZrNiZPz

BaPt,As,

structures).[l361

(Reproduced

a cyclic

both

atoms

crystal

and boron double

and

bond

phosphino-

dimer

(691,

carry

bulky

rather

29

Me Me Cl

CEt,

/ N-B \

PH-CEt,

Me

G

P/

Me

Et&

(68)

He Me

substituents.[l401 monomeric than

the

Four

with single

membered

mesityl.

On the other

a P-B bond

PzB,

and As,B,

by treating

(191.6pm).[1421 RP(H)B(Cl)R'

the absence

compound

also

trigonal

when

ring compounds,

with

shows

contains

bipyramidal

to 160°C;

P-B distances

R'BCl, that

of RPHLi

(Pr' ,N)BCl.P(SiMe,),

of solvent

with

RMLi,

Reaction

which

An unusual

is

substantially

shorter

P-B distance.[l411

for the phosphorus

positions

Ph,PB(mesityl)z,

185.9pm,

R' = 2,2,6,6_tetramethylpiperidino

be obtained

isolated

hand,

length,

a single

for R =

and M = P or As, can but an X-ray

the P-B bond

with

R'BCl,

structure

is single

similarly

yields

B-N bond.

P z B 3 cage and

(RMBR'),

compound

(Pr' ,N)BCl=

the phosphorus

of 196.9pm.[1431

(70) has been

are

atoms

heated occupy

in apica

30 Me7

Me2 P-

""\

/

\

/ Al

(Me,Pl,Ni \

Ni(PMe,l,

/\ CHz

P -

Electron

diffraction

with

data

data

Al-P-Al

from

showing

angles

131.7

of exocyclic

and Me,AlH

isomer

is an

groups

of

Al-P

results

mixtures,

mixture

been

distances

and 96.4".

(MePhPAlMe,),

compound

MePhPH

have

(Me,PAlMe,l,

(C,, ) model

and P-Al-P

the product

orientations

for the trimer

A related

is eliminated

suggest

Me,

of a chair

respectively.Il441 benzene

/ P

CH Z-

Me,

on the basis

of 243.4pm

/A1\ CHz

P -

Me,

refined

MeZ CH,-P

CH z?-----P

2

and

when

spectral

due to different

and different

ring

conformations.[l451 The major Ni(CODlz chromic New

cyclic

gallium

Bu"CH 36Z with

product

in pentane

of the reaction

formulated

dimer,

phosphides

three

mols

two mols

of Bu',PLi

Reactions

of RLi

A1(CHzPMe,l,.

is a yellow,

PMe,

and

thermo-

(~1.[1461 as Ga(PRX),,

have been

THF at -78%.[1471 and

as

formulated

andX=Bu"orH,

either

between

at low temperatures

prepared

where

or But,C,H,P(H)Li

of CaCls

(R = Me or Bu").

with

R = But or

by treating

in toluene

one mol

on the other

CaCl, or

of ButzPLi

hand,

give

dimers

(R,CaPBu",l,.

5.2.3 As

Bonds

before

Bonds

4 Elements

compounds

are considered

between

phospha-alkyne P(SiMe,lJ

bonds

reviews,

phosphorus(V)

species

and

to Group

in previous

Carbon

and

in each

section

are treated multiply

bonded

first.

A new approach

and Phosphorus(III1.

synthesis (equation

intermediates.tl481

to phosphorus(III1

uses 10).

Loss

the reaction in which

between

acylphosphines

of (MeJSilzO

occurs

acid

to

chlorides

are probably

at 120-160°C

in the

31 RCOCl + PtSiMe,),

-t I(Me,Si),P-C1O)Rl

+ Me,SiCl

. . . f 10)

\ -(MeJSi),O
CH,8u’

presence

of

Me,SiP=CR(OSiMe,f

. etc.

sod ium hydroxide

phospha-alkyne

which

reactions

CHzN,.

The the

with

synthesis

sole

of

product

173).[1491

The

can

be

the

to

give

the

appropriate

by cycloaddition

etc.

first

triphosphabenzens

reaction

compound

catalyst

characterised

MeN,,

the

of

as

is

air

of

(72)

PmCBu* and

and moisture

the

is

diphosphete

sensitive

(Me,NjZP

reported and

zzr-CH

I

I

HC =

P(NMe,Iz

(75_) contains

an almost

170.2pm)

and

undergoes

one

planar long

Diels-Alder

bond

ring

with

(175.8pmJ.

reactions

with

five

short The

cyclic

P-C

bonds

(mean

phospha-alkyne 1,3-dienes

also (741,

as

32

R'IR" = H, Me. Ph: X = 0, P(S)Ph, etc.) to give unstable adducts which decompose to A"-phosphinines

(75).~1501 0 1-Bonding by both PSZBu' and PaC{adamantylI has now been

observed in a series of compounds formulated as shown Ph

or

4-Me&H,;

M = MO or W).I1511

in

(3,

R' =

The structure has

Et, been confirmed for the adamantyl derivatives (76, R‘ 3 Et and M = Mo) by X-ray studies, which show short Ho-P and P-C distances, )1"-U2 behaviour on the other hand 230.5 and 152pm respectively.

cocp

I

BU

)--_ 0

P

P

------L f&l”


Bu" (79-l

(78)

is found in the complex anions reaction of PSBu"

with IMnH(COf,,

iMSH(COl,(P~CBu')lI-

isolated from

where M = Fe or I+~.[1521

PsCBu' dimsrises on reaction with C~CO~C,H~)~ to give successively

the complexes (~I-(~),

[I531 and a second group of

workers have widened the scope of the reaction by using a range of ethylene complexes,

IM(C,R,)~C,H,),I where R = H, M = Co or Rh and

R = Me, H = Co, Rh or

lr.11541

The products are confirmed as

33

complexes,

(C,R,lM(PCBu”PCBut),

1.3-diphosphacyclo-butadiene R = Me and

M = Co.

equivalent

P-C

P&C,

of

the

an

X-ray

ring

is

previously

(801

is

obtained

[Pt(dppe)(PmCBu”)l on

as

the

coordinated

a

CHPH,

In

minimum,

[156,1571 the

were

first,

some

43

photolysis states

of and

in

R,PCR

where

best

the

fact

Further and

In 0 are

are

as the

also

participation

significant

as

insertion

the

[I581

reactions

of

(HP=CHMel.

the

H,mH

and

MeP-CH,.

isomer

with

The vinyl

between

carbon

calculations to

also key

latter

phosphine

CH,P.

was

support

have

in

is

ground rather for

with

a

comparison

the

conclusions

small

but

becomes of

the (PH)

isomeric

with

the

calculated least

is

X increases.

problems

vinyl

than

HPXz

Among

attacked

and

the

singlet

calculations together

the

and

global

the

X3-phosphinocarbenes

is

CH,PH

the

intermediates

electronegativity

the

for

singlet

phosphinidine of

stable

of

0

initio

HPX.

have

characteristics phosphirane

\

corresponding

second,

that

calculations

C

ab

given

electronic

HP=CHMe

\

they

analogues

d orbital

reaction

Bu”

calculations

species

two-coordinate

increasingly

with

Re(CO)4

below

considered

NH or

X = CH,, the

/

phosphinodiazomethanes;

are

the

phospha-ethene

kcal.mol-’

X5-phospha-acetylenes.

with

minima singlet

The

that

C

reported

local but

methylphosphinidine. proposition

\

have

identified lying

with

phospha-alkyne.[lSS]

Phz

groups,

product

planar

consequence

Ye\ p,pt, p,

Two

the

(CO),

Phz

CH,P .

of

essentially

p\ c

attack

unknown

study

lengths.

complex

and

monoxide

The

bond

A phosphinidine [ReH2(COl,I

by

of

addition

ethylene

and

the

phosphine

phospha-alktnes as stable.

being

the Valence

most

34 isomerism

in phospha-alkenes

problem

of cycloadditions

between

phosphorus

Almost

has been

with

or arsenic

quantitative

compounds

yields

to proceed

can be obtained

elimination

when

it reacts

dienes

product

phospha-alkene,

with

addition

by photoelectron

Me,SnP(C,F,),

of protonic

double

bonds

yields

Direct

condensation

to give species

chiral

4-RC,H,CHO

benzaldehydes, of catalytic

of Me,PC1.[1621

is heated

at 300°C

HX. for X = OMe,

where

new

by Me,SnF

and

lOWa torr;

products

and

Br or NMez,

to the

C,F,P(X)CF(CF,lH.[1631

Bu' ,C,H,PH,

p-toluenesulphonic

has been and mass

The

results

[2+41 cycloaddition

phosphines

between

MeP=CH2

spectroscopy

C,F,P=C(CF,)F,

of the

the reaction

intermediate

2-Phosphapropene,

as a pyrolysis

bonds

by photolysis

via the phosphinocarbene

in the gas phase

spectrometry

X3-g2

(Pr',N),P.C(N,).P(NPr',)z;

(Pr',Nl,P+=C-P(NPr',),.[1611

perfluorinated

containing

of the phospha-alkene,

bis(phosphinoldiazomethane,

identified

11591 as has the

and carbon.11601

(Pr',N)P=C(NPr',)[P(NPr',)21,

is considered

reviewed,

and

substituted

R = H, OMe or NMe,, acid,

also

leads

in the presence

to

phospha-alkenes.11641 The E and

Z isomers

R = Ph, SiMe,

and Br.

crystallisation for both

169.0

and

angle

77.6

phase

NHBut, and

with

190.lpm of

respectively:

NHSiMe,,

NEt,,

agree

two conformations

with

here

N(SiMe,),. with

from n(P=Cl U.V.

data.

differing

to the molecular

aminophospha-alkenes.

system

Both

in the dihedral

form

MNDO

C-P distance

a

in the angles

of

is 189.8pm.

R = Cl, F, OBu',

etc.,

have

been

assigned

calculations.[l681

Depending

phosphorus

on steric

in the orientation symmetry

give

with

and P-C-P

and non-bonding

isomers

investigated

(CF,PCF,l,

where

Me, Bu".

parameters

respectively

C-P-C

the mean

angle

for CF,P=CF,

dimer

with

determined

show major

measurements

for RP=C(SiMe,),,

in conjunction

potentials

respect

ring

been

has molecular

The cyclic

for

ring.

for the P=C and P-C bonds

p.e.s.

electrons

and

for the monoclinic

diffraction

has a puckered

discussed

have which

angles

at -125°C

and Bu',C,HzP=CHR,

by fractional

Structures

and the phenyl

108.8°.[1671

and He-I

Ionisation

with

those

Electron

and 95.6"

U.V.

separated

and C-P-C

bond

Me 362 C H P=CPh,

identical

C-P=C

been

of Bu" ,C,H,P=CHPh,

in the P-C-C

earlier.[l661

gas

forms

the P=C double

Orthorhombic almost

have

and HPLC.11651

isomeric

differences between

of But ,C,HzP=C(SiMe,)R

plane,

requirements,

of the amine are

are present

possible in

group for

35 Pr’,NP=C(SiMe,l,

and

explanation or

NR,

for

conformational

differences

in

isomerism

n.m.r.

data

provides

for

an

species

carrying

NHR

substituents.

Continuing systems,

exploitation

a

conjugated reaction

stable

between

Me&ii-S-C

sequence C&.

of

relationship

has

and

such

as

S /C-SiMes

and

be

P=C

a

synthesised

in

a

Acyl prepared

a

\\

p\

can

C-C

containing

been

Me,SiC1.[1691

(82)

P

I,

between

181).

atoms,

LiP(SiMe,),

phospha-alkenes

-

the

1,2,4-thiadiphosphole

P=C-P=C

substituted

of

by

OSiMe, i \P C/ II 0

(82)

a

COCI

COCl

(84-l

tresting

a

1,2-dicarbonyl

methylsilyl)phosphine; however

the

structure.[l701

Ii?+21

dichloride with

cycloaddition

such

phthaloyl product

as

(83)

dichloride, (84)

with the

confirmed

trisftriproduct by

an

is X-ray

36 The

benzazaphosphole

distance

of

169.5pm

is isotypic compound

structure and a small

(851 is characterised (88.2")

with

the arsenic

analogue

because

of hydrogen

bonding

HX addition phosphines

to the double

CF,P(H).CF,X

alternative

formation

when

CF,P(X).CF,H Water

AsMe,.[1721

has been

is in fact

observed

clust er has been and B,H,-.[1731

Two equivalents

phospha-ally1 converted

of ozone

isolated

are taken

PhP=C(NMe,l,

can

to give

or PMe,

reverse

to the dioxygen

product

or to the SeMe

of

up by the electron while

of

A new

from a reaction

c&J,

rich

the substituted is similarly

A complex

(87).[1741

or

with

addition

of OR-.

(Me,N),C=P-C(NMe,)(=N'Me,),

cation,

lead to secondary

pH dependent

in the presence

ClP=C(SiMe,l,

the nitrogen

X = Cl. Br, SMe,

at pH > 13 and

heteroborane

phospha-alkene,

when

by a P=C the compound

latter.[l711

X = OH, OR, NR,

addition

angle:

but not with in the

in CF,P=CF,

products

of CF,P( OH).CFzH

alcohols

bond

C=P-C

reaction,

Ph

1

/NMe,

OZP-c

\

I

N-Me,

0

invo lving

both

bond , occurs

Si-N

when

cleavage

secondary

(Me,Si1zNP=CHSiMe,.[1751

and addition amines

With

react

across

the P=C double

with the products

diethylamine,

(88) or the unexpected P(III)-P(V) species reactant ratios. With carbon tetrachloride,

are

either

(89) depending

the

(88)

H

NEt, \ N -P

Me,Si

/

(Me,Si),N

/ \

\P-P

(88)

oxidised Three phirane

//

NSiMe,

-

Me,SiCH, '

CH,SiMe3

NEt,

'CH,SiMe,

(89)

to Me,SiN=PC1(NEtZ)(CHZSiMeJ). products, 1%)

i.e. the complex

and a complex

of the

(901, a functionalised latter

on

is smoothly

(921, are obtained

diphos-

37 when

the

hydride

anion

[HFe(COl,l-

is

added

to

pure

Cl

H\P=C(SiMe,lz

/

‘P--P

ClP=C(SiMe,1,.[17

CH(SiMe,l,

‘Cj

1 Fe(C014

(Sille,),

Cl

CH(SiMe,l,

/

‘P-P ‘C

’

‘Fe(CO1,

(SiMe,),

Recent

work

has

shown

methanol

with

diazomethane

1-alkyl-1-methoxy

that

3,5-diphenylphosphinine and

derivatives

R’RYN,

substituted

ether,

spec i es

in

methylene The

which group

two at

distances extended

to

nickel of

and

(931

phosphacyclohexene in

from

183.2.

Huckel

to

in

give

solvents

such

give

a complex

rings

are

polycyclic

bridged

by a

phosphorus.

phospha-alkene

bonded

reacts

(94) diazomethane

however,

species

In aprotic

(941.11771

(93-j as

(931

(bipylNi[P(2.6-Me,C,Hs)=CPh,).THF

an X-ray

217.7

calculations

study

and

showing

198.7pm point

to

P-C,

is Ni-P

respectively,

and

11781

n’-bonding

n2-

Ni-C but

in

[MeP=CMelCr(COl,.[l791 Phosphinidine oxidation

state

(RP:)

chemistry,

transition

metal

stressing species

the has

involvement

been

in

reviewed,[l801

low

38 and

a short

transition of open The

review metals

and

is available and main

closed

reacts which

phosphorus

with

ethanol

whereas

e.g.

one mol

excess

of the

giving

(951.

doubly

group

fragments,

of CD,OD

the formation

CpMo(COlz[n'-P=C(SiMeJ)zl,

bonded

to both

the metal

and

carbon,

CpMo(COl,(n'-P[CH(SiMe,),lOEtl

is a three-electron

gives

leads

between

including

Pr' ,NH and C,F,SH

CD,OD.

reagent

bonding

complexes.Ll811

complex,

to give

the phosphido

electrphiles,

group

phosphinidine

phosphavinylidine

containing

on multiple

in

donor.[1821 react

Other

similarly

but

CpMo(COl,{=P(OCD,l[CD(SiMe31zl)

to reaction

W ith nucleophiles

such

at the Mo=P

as NaOMe

bond

an

also

in THF the product

is (961.

SiMe,

OCD,

CP

\

/

OC-

\

/

MO-P-C-SiMe= /I D

oc

I-

CP

OCTMOF,

\ \ OCD,

-CC(SiMe,l,

oc

D

OMe

(961

(95)

Phospha-alkenyl acyl

chlorides

proceeds

complexes as shown

can be obtained.

in equation

via CpFe(CO),P(SiMe,l[C(OlRl

CpFeXCO)nP(SiMe,l,

+ RC(OlC1

for example,

(11); the reaction as an

using

probably

intermediate.Ll831

-+ CpFe(COlzP=C(OSiMe,lR

. . (111

+ Me,SiCl

R =

Bu',

Ph or mesityl.

In a similar

it has been

fashion,

Cp^Fe(C012P=C(OSiMe,)(mesityl) Cp'Fe(CO),P(SiMe,l,

1. can also

possible

as the sole

reaction Mono

chloride.[l841 Scheme

with

and diacyl

the

is similar

iron carbonyl

product

of the

phosphido

complexes,

as shown

in

be obtained. (97, R = C,H,Bu',)

Bu" z,C,Hz.P=CHPCl(C,H,Bu', 1 is treated

its behaviour

to isolate

2,4,6-trimethylbenzoyl

A 1,3-diphospha-4-tungstobutadiene when

9

complex

to that

with

of butadiene

(981 the

ligand

results

Na[CpW(COl,l; as on conversion

changes

conformation

to from

39

trans. to cis.[1851 PhCOCl > I

Cp"Fe(COf2P=C(OSiMe,)Ph and Cp"Fe(CO)zPfC(0)Phl,

Cp"Fe(CO),p(SiMe,),

Acyl chloride Cp"Fe(COI,PHIC(O)Rl ,Scheme 1

\ OC-W--P

/R \

/ OC

\

oc - ,@
CH=P 'R

Styryl substituted diphosphines RPCtfCH=CHPhl, where R = Bu*&,H,

OC

(CO),

(99) can be obtained by treating or But, with either Bu*Li or

magnesium and the tri-t-butylphenyl substituted compound undergoes Ally1 a Cope rearrangement to give the phospha-alkene (~).[1861 Grignard reagents, R~H:CH.~H*Mg~l

(R = Me or Ph), react with Ph

Ph

40

R

\P_P-R

L/

(101)

(102)

RP=CH-PClR (101)

(R = C,H,But J) to give

which

via a Cope

dynamically

stable

R = C,H,But,), undergoes

R’

rearrangement

product.[l871

obtained

valence

1,3_diphosphahexadienes give

by treating

isomerisation

(E),

the thermo-

The diphosphahexadiyne, RPCl(CsCPh)

to give

with

(103,

BuLi,

the cyclobutene

derivative

(104).[1881

4

R

R

CPh

/p\ CPh

(104)

(103)

Reaction (12).

of RP:C:O

gives

RP:C:O

+

a series

(R = C,H,Bu*,) of new

Ph,P=CR'R=

with

an ylid,

1-phospha-allenes,

-+

RP=C=CR'RZ

shown

in equation

but although

+

Ph,PO

. ..(lZ)

R' = Ph. H R' = Ph, CO,Et

(Me,Si),O product Treatment

is split is a dimer of the

diphosphines.

out when (-1

same

Ph,C:C:O

rather

than

phosphaketene

(Me,Si)R'P-PR'(SiMe,)

reacts

with

an allene with where

PhP(SiMe,),,

the

derivative.11891

bis(trimethylsilyl)R' = SiMe,,

Ph or Pr',

41 OSiMe, Ph Ph,C =C

P -

c =

1

1 P--h

-

CPh, R-P

bC’PRV I

(105)

R-p%/PR’ I

OSiMe,

gives the

tetraphospha-I.5hexadienes phenyl

The the

compound

has

l-phospha-allene

complex

Ni(C0)4.

(106)

been group

prepared

is

and

a u,-nZ-bonded

in

the

low

obtained

from

r)‘-bonded

by treating

11911

stabilised

yield

a reaction

the

structure

to

of

an Ni(COJJ

Bu%,C,H,P=C=CPh, Bu”P=C=CHPh

product

of

and

determined.tl901 group

in

with

ligand

has

been

[Bu”P=C=CHPhlFeCo,(C0),

[PBu”(CmCPh)HIFe(CO)4

with

co,(co),.[1921 Enantiomers

of

the

axially

HPLC using

a chiral

racemisation

occurs

the

dissymmetric

have

But,C,H,P=C=PC,HzBut3

been

phospha-allene

separated

for

the

first

time

(+I-poly(triphenylmethylmethacrylate) on exposure

to

light

but

by

column:

only

very

slowly

in

dark.11931

X-ray allene

structures

are

complexes.

(R = C,H,But, K[CpNi(CO)I

)

and

obtained

reaction

in

first

be

two and

new nickel-1,3-diphosphaINi(CO),(RP

RP:CH.PRCl

has

also

+ 2RLi

been

CH

with,

in

high

structure

of

yield the

PR) I,

respectively,

been

the

Me,SiCmC

equation

produced,

from

A l-phospha-

determined.[l951

containing

both

(14),[1961

P==P and

-t R,P-C(SiMes)2-P-C(SiMe,),

PhCmC or

+ Li(Me,SiC=C=CR’z)

obtained

the

(13): has

triphosphabutadiene,

R = Me,SiCIC. RPClz

can

product

2C1P=C(SiMes)=

PR)

Ni(C0)4.[1941

equation

1,2,3_butatriene

for

CH

by treating

Diphospha-1-butenes substituted

available

CpNi(RP

P=C bonds + 2LiCl

and in . ..(I31

Ph -9 RP=C=C=CR1a

+ LiCl

+ MesSiC1

. ..(14)

the

42 R' = Ph. SiMe,

R = Bu",C,H,

OSiMe,

/

OSiMe,

RP=C,

base )

‘PC1

/

RP=P-C

+ CO

. . (15)

t 2Me,SiCl

. ..( 161

+ Me,SiCl

* 'PR

RP=C:OSiMe

3

R = Bu",C,H,

OSiMe, / \

%

P(SiMe,),

results

conjugation,

/

-+ RP=P-C

+ RPC 1,

RP=C

from

OSiMe, PR in

the reactions

equations

(15)

and

(16).[1971

Two mesityl lithium

derivatives,

with

structure

salts,

pyramidal

have

also

all have

sequence

of solvated

phosphorus

atoms

state

be present

obtained

containing distances

A four-membered phosphido either

ions and PR,

based

ring.

which

different

The

coordination from

those

and

the

thought

to

of the

latter

has been

(1071 has been a slightly of 258.2

ring

complexes

SnClz

Mg(PPhH12.TMEDA

is also

found

puckered

and

determined. for

four-membered

172.2pm.

present

can be as meso-

in the tin(II1

(108, M = Sn or Pbl obtained

or PbCl,

with

three

mols

ring

respectively.

of LiPBu",

and

by in THF

solution.[2021 The Pr'

addition

or But with

by

on an alternating

groups.[l99]

tetrahedral

is a

lithium

N-tetramethylethylenediamine

structure

(Ph,Pl,CHLi.TMEDA

lead{111

Li,P,

[Li(THFIP(C,HI,l,l.

but the monomer,

with

the structure

treating

on a planar

latter

solutions.

with [2011

while

for the following

structures

are clearly

is polymeric

and C-P

and

the dimeric

in distorted

on treatment

Li-P

their

The

is based

chain

and

at phosphorus

[Li(THFl,PPh,l,

lithium

are

A monomeric

(mesityl)PH,

synthesised.[l981

determined

infinite

in ether

rat-forms:

[ZOOI

salt

been

structures

Mg(PPhH1,

and

been

geometry

[Li(OEt,lPPh,l,

contrast

solid

have

of the dimesityl

Structures

and

[Li(OEtzlP(mesityl),lz

[Li(THFl,PH(mesityllJ monomer

(mesityll,PH

phosphines.

compounds CpW(COl,Cl

of secondary

phosphines.

can be dehydrohalogenated

R,PH

where

to give

R =

43

/p\

But,P-M

Li(THF)

\/ P NMe,

Me,/"" 2

\ H&

I

(108

-CHz

1

(107)

CpW(CO)z=PRz 228pm) Three

using

following different

treating

REClz

W,.[2041

The

(OC) 5 M'E\

DBU,

with

the double

from an X-ray types

bonded

structure

of product

interrelationships

M(CO),

have

these

(OC)sM

has been

M(CO),

(110)

R\ /“(oc)5 /E=E\ R

(111)

obtained

(0C)sW

(OC),W

\ /,, /,,\ -

W(CO),

(112)

by

(M = Cr, MO or

species

/E\

(109)

(OC)sM

been

Na,[M,(CO),,I

between

(W-P

determination.[2031

(m)-(m)

(E = P, As or Sb) with

structure

44 Cr(CO),

“\ /

As =As

P

\1 (‘OC)

Fe(OC),

,Fe

'Ph

"(CO),

(114)

(113)

But\

(Me,Si),CH

Mo(CO)s \AssAs' \

CH(SiMe,),

Bu"' (116)

(115)

R

R

,

I

Ph-P (OC ),Fe/

/

p-P

Fe(CO),

p

Fe(CO),

P-Ph

I (OC ) ,Fe’, \

t-7

s-i

(OC)3Fe

-

Fe

I’ /\ /

!i

I3

(117)

discussed (111,

PBu'H),I which

in conjunction

gives

contains

represented with

CO, C,H,

New cage among

oxidation

X-ray

[Fe,(CO),(PBu"),l a short

and C,H,

the products

and

Fe,(CO),,(PR),

with

(117)

of

species

better reacts

structures

CO and C,H,.

for R = Me, Ph or tolyl,

reactions,

treatment

type

The compound

into the P-P bond;

products

for

[Fe,(C0)6(V-

is probably

complex.[2051

of various

of

a tetrahedrane

(206pm)

by insertion

of Fe,(CO),(PHR)2.

determinations

Oxidation (-1,

P-P bond

for the reaction

compounds,

structure

(m)-(m).

as a diphosphene

are available

are

with

E = As. M = WI and

including

tFe,(CO)n12-

the with

RPCl,

45 and

reactions

of

iron

[Fe(C0),12-.I2061 and,

of

the

Treatment liquid

of

into

(118)

of

containing (117,

was also

with leads

(~I.12071

of

the

PhXP.CH,.PXPh,

been

to

with determined

structurally.

successively

Cl,P.CH,.PCl,

type

bonds

has

investigated

1.2-diphosphinobenxene 1,2:dichloroethane

P-Cl

R = Me)

and

phosphine

compounds

species

structure

by-products,

ammonia

tertiary

carbonyl

The

sodium

the

polycyclic

has

been

converted

X = Cl,

H, Et,N

where

in

Ph

etc.,

and

the

products

The the

when

PhPLi.CH,.PPhLi

are

the

phosphetanium

phosphenium

addition

of

reacts

phosphorinane salt

(121)

with

1.2-dihalogenoethanes

(m).[2081 is

obtained

from

[Pri2 NPC1]‘[A1C141-,I2091

salt,

a C-H bond

But 3 C6 Hz PC~(SC,H,BU”~)

of

a t-butyl

is

treated

and

substituent with

(122)

when

AgSbF,.[2101

(122)

Structures

have

determined

naphthalene

are

readily

providing

the

unsymmetrically

PhHP(CH2),PPhz thiazaphospholidine

and

for

two

bulky

phosphines,

But 362 C H P-O-CH,-CH2-b.[2111

bonds

Aryl-phosphorus of

been and

But,CsH,P(SiMe,),

a number

and

oxidative

gives

(121)

sodium

cyclooctadiene

cleaved basis

substituted

MePhP(CHZ),PPh,, (123)

is

produced

for

on treatment convenient

diphosphines, where

such

n = 2-6.12121

by treating

with syntheses as A new

dimethylthiourea

of

46 with

acetylene

compound

bis(phosphonous

can then

phosphorus

dimorpholidel

be oxidised

by elemental

Furfuryl

atoms.[2131

R,PC%PR,: sulphur

phosphines

the

at both

(124, R = Ph. mesityl,

P

Me-; - F>c=c
s

PR,

(123)

Ph,P-CH, (OC),W

(125)

(126)

Me,

Bu' or CH,C,H,Ol

W(CO1,

units,

is lost to give coordinated Sodium in ether phosphine Sulphur isomeric (1281

(1251 can coordinate

(1261

in which

in ether a furfuryl

gives

at ca. -20°C oxide,

tin

carbon

is weakly

to monoxide

n2-

adds

to the novel

P-sulphides

are

to give

respectively

while

on treatment reported

between

spirals

react

with

Ph2P[OC(OlC,F,l

Ph,PCl

and

the

Ph,P(O)C(OlCF,.[2151 2.2'-biphosphole

with

the hexacarbonyl.[2161

lithium

is in distorted

and

a-membered

ring

iron

two

complex Further

chloride

2 and tin(IIlbutoxide

(1301.

which

pseudotrigonal

in an equatorial

of the Mo(COl,

giving

(1291.

intermolecular

phosphorus

to give

one form

PhP(CH,CH,SH)

from

(1271

only

with

the new heterocycle

infinite

ring

and trifluoroacetate

bis(Q5-diphosphafulvalene)diiron Reaction

via phosphorus

solution,

to tungsten.[2141

pentafluorobenzoate

results

reactions

and

and on irradiation

Sn...S

(Sn...P

in toluene state

forms

contacts.[2171

bipyramidal

position

is in the boat-boat

in the solid

coordination 261.4pml

conformation.

The with

and the

47

P Ph

P

Ph

(127)

(128)

\\

\ ‘S

/

Fe

Fe /’

A series of new polyphosphorus

2 \

/I l/J

PPh

S

ligands (see Scheme 21 has been

synthesised by addition of P-H species to the double bond in (Ph,Pl,C=CHz; the compounds are expected to lead to a wide range of different transition metal complexes.12181

Further reactions of

secondary phosphines R,PH. for R = Me, Pr'. But. Ph, etc., with R'P(CH,CH,=CH,l,

in the presence of azobis(isobutyronitrile1

and

with UV irradiation show that the reaction is not general, but it has led to the successful preparation of the two new ligands, Bu'P(CH,CH&H,PPh,),

and P(CHzCHzCHzCHzPMe,1,.[Z191

Entry into a

new class of 1,4-diphosphacyclohexanes

(1311 is possible following

addition of Me,SiPH, to Et2NP(CH=CHz12

in the presence of AIBN.

The product is interesting as it contains two oppositely polarised phosphorus atoms: an acyclic species, CHz=CH.P(NEt,l.PCH,CH2PoSiMe, is also obtained.12201

48

phzpY PPhz

PhJ’

Fh

PH 2.

\

Ph,P

PhzP

pAp Ph,

Ph,

Phz Scheme

2

Phz

Ph,

Phz

Ph,

Ph,

49

Continuing been

and R,PH were

this

synthesised

theme, from

a range

vinyl

R = NEt,.

polyphospha-alkanes

methyl

(R = Me, Pr' or Phl.12211

R,P(CH,),. PMe.(CHzl,PMeH.

(where

of linear

or ally1

Among

phosphinic the compounds

PMe.(CH,l,.PPh.(CH,),.PMe.(CH,),.PRR' or OMe and n = 2 or 3). with

A surprisingly

easy

phosphinolallene

is shown

+ BuLi

3Ph2P.CmC.CH,Li

PMe, where

synthetic

can be oxidised

Ph,P.CxC.Me

route

in equations

have

-I Ph,P.CmC.CH,Li

-t

sulphur

n = 2 or 3.12221

(171 and

(181;[2231

with

the

bis(trimethyl-

. . 9(171

+ BuH

(Ph,Pl&=C=C(PPh,lz + 3LiCl

and

R, R' =

FeLCl=,

to tetrakisfdiphenyl-

to the tetraoxide

+ 3Ph,PCl

silyllperoxide

(where

Iron complexes,

the tetraphospha-alkanes,

Me,P.(CH,l,.PMe.(CH,),.PMe.(CH,),.

compound

isolated

OH, or H and n = 2 or 31 and

RR'P.(CHzl,.

isolated

has esters

R,P(CH,),.PMe.(CHz),.PMe.(CH,),PR,

Me, H, NEt, been

acid

and

selenium

+ 2PhzP.CmCMe

also

. ..(18)

add to give

tetrachalcogenides. A novel zig-zag

ligand,

P, chain,

phosphinolmethane coordinates four

piperidino,

Treatment

atoms

such NHBu*

prepared

morpholine

and bistdiphenyl-

react

atoms

derivatives,

been

containing

is formed

to cobalt

phosphorus

phosphorus

PhzP.CHz.PPhz.P,.PPh,.CHz.PPh2. when

with

white

The

Co(8F41a.[2241

in a distorted of the opened

of the dppm

phosphorus

octahedral

and

A series

units.

as RIRZP-CmC-PR'RZ

where

ligand

arrangement

P 4 molecule

structure

via all

two of the

of acetylene

R' = R2 = morpholino,

or F and R' = F, R2 = morpholino

and an X-ray

a

carried

or NEtz,

has

out for the tetra-

derivative.12251 of triphenylphosphine

disproportionation dichloroethane

and

solutions

isolation and

with

iodine

of crystals

[PPh,IIIs,

with

leads of

to

iodine

[(PPh~11,1,11,

the same

empirical

from

50

from

formula. zig-zag

chains

of

"molecules"

intermolecular gives

strong

which

infinite

Iodine

shows

parallel.

layers

of I,- anions

interaction

chains

oxidation

isostructural

[(AsPh,IlzI,II,,

between

cation-anion

yield

contacts.

diffraction

units

[(PPh,I)z191'

while

for the former, gives

X-ray

toluene.[2261

with

in the

latter

by further

of triphenyl

arsenic

the phosphorus

compound

above.

n = 1-4, formed

phosphorus Solid

diffraction phosphine

when

silver

31P n.m.r.

point

group

lanthanum

Ph,As

tris

have

been

decrease

like species.[230] PhP(CH,PPh,lz

complexes

from

as,

and

(1321 and

The

isomorphous

is ionic with

complexes

respectively,

the

with Cu,Cl,L,, In the

[AgzLzI[BF,1,.[2291 isolated the

in THF,

X-ray

nitrate-triphenyl-

and AgBF&

(1331

behaves

and

as an

can be prepared [2311 and although

involve

CH, Ph,PCH

from LaCl,

ligand

Ir, complexes

and PhAs(CH,PPh,l,,

with

crystal

n = Z-4.[2281

are

CuCl

[La(Ph,P.CH.PPhzl,l,

of K[Ph,P.CH.PPh,]

both

M = P, As or Sb

for n = 2 and 3 but

ring,

mols

single

of silver

formulated

an eight-membered complex

and

complexes

complexes.

0~-1~-allyl

Mo(C015

where

in ethanol,

where

coordinated

n = 4; the bis and

contain,ing

spectroscopy

Ag(PPh,l,NO,.

is weakly

Pr',PCHzPHPr'(Ll

with

nitrate

to the formation

complexes,

corresponding

three

from

to antimony. [2271

state

nitrate

[Ag(Ph,Ml,l'

of the complexes,

Stabilities and

donation

the

via

-0 0

/ PhP

0

\ CHz

(132)

-0

(133)

phosphorus which

initially,

oxygen

Phosphorus numbers, of this

and

also

irradiation

donates

containing

Ligands

tetracarbonyl

species

in

to the meta1.[2321 ligands

the following

review.

gives

continue

are among containing

to be synthesised

those

noted

pyridyl

i.e. 2-CsHsN-(CH,l,-PHR

positions

to phosphorus,

or Ph and

n = 1 or 21, are now available

during

groups

in large

the period

in a- or B-

(R = H. Pr',

and the presence

But

of a PH

51 function

allows

further

reaction

[~-c,H~N-(cH,~,I,PR.[z~~I have

been

to

A range

described

with

give of

NPN donor Ru(IIl

and

PhCH,N(CH,CH,MPh,l,

ligands, (III)

complexes

where M = P or As,

12341 and the rigid tridentate ligand (Ll (_134) has been synthesised

from

of

[MLClICl.L’

complex,

EtOHl each

Ph=PCl

and 2,6_diaminopyridine.[2351 (for

and mer-[ML(COl,1.2THF type,

(135)

tridentate

and

chelate

Ph,Py

M = Ni, (for

(136).

L’

= H,O;

M = Cr.

contains

MO or

an almost

Two types and M = Pd, Wl are

L’

=

formed:

planar

system.

YPPh, H

H (134)

Ph,P

-

Ni -PPh, ;1

R

HN

f

NH

IT/ I

Ph,P -MO

HN

h

HN

PPhMe

PPhMe

-PPh,

\ I

co

co (136) Tetra-dentate chiral

phosphorus

(137) ligands,

L,

centres,

(137. are

R = H or

Me),

now known giving

containing three

two

forms of

the

cobalt complex, [trans-CoClzL1+ and four of the cis complex, [Co(acaclLl,', which can be separated by column chromatography.[2361

Anhydrous chromium(II1) chloride gives a 1:l

complex with the tripod ligand MeC(CH,PMe2),, which contains a facarrangement of the three phosphorus atoms.[2371

With chromium(II1

52 chloride giving

on the other

in THF,

which

trans-CrCl,L,,

hand.

the

ligand

can be reduced

is only

with

bidentate

sodium

amalgam

to

CrL,. New

tripod

(where

PMe,),_,

MeSiCl,Vi,_,

when

o-xylylene

x = O-21,

with

Cyclisation occurs

MeGe(OCH,PMe,l,

ligands,

have

prepared

from

MeCeCl,

or

Me,PCH,OH.I2381

giving

complexes

the di-secondary dichloride

template.[2391

been

and MeSi(OCHzPMe,),(CH,CH,-

react

The

of the tetradentate phosphine,

in the presence

product

macrocycle

MeHP.(CHzlz.PMeH,

is a mixture

(138)

and

of a Pd(II1

of three

diastereoisomers

cone> OL.9 kH,l,PPh,

-\ / 52 r” “?

OL-NJO I

CH,PPh,

(139)

which (RSRS)

(141)

can be crystallised isomer,

Practical oxa-phospha hard-soft

with

synthetic

from methanol

palladium routes

macrocycles binucleating

in square

to give pyramidal

are now available

(139.

the pure

coordination.

to the aza-phospha

X = NH or 0). a new class

ligands.[2401

syn-

and

of

and to the phosphino-aza

crown

53 ethers

(140.

transition

metal

aza-crown

Bonds the

between

via

the

Carbon

and

ylids

X =

H,P=CXY

Y = H.

dissociation

energies

of

over

The atom

latter

and

CF,.

into

PHJ

the

The

bis the

synthesis

Ab

isomeric

point and

50kcal.mol-’

including

t2431

Phosphorus(V). and

The

studied,

(143).

(m).[2411 phosphorus

F or

H,P=C(CF,),.[2421 been

and

an

can alkali

to

:CF=; for

initio

low

binding

this

energy

both

H3P=CHz

at

the

and

coordinate

to

reactivity

as

has

been

reviewed

(X

= 0,

S or

either

phosphorus-vinyl

equation

summarise

for

three

\

yield in

A product R = Bu”

of

or

suggests

ylids

(19).[2451

high

Ph.

discussing,

Se),

Bu’,C,H,P(:S),,

RP(:NR’)(:NR2).[2441

photochemically

bis(methylene)phosphoranes. 64pm.[2461

and

experiments

produced

see

(21)[2471

Se).

trapping

phosphinocarbenes regarded

species

= S or

from

acetylenes,

also

(143)

(X

Evidence

of

NPlc/

7

(mesityl)P(:CPh,)(:X)

RP(:NR’)(:X)

has give

I

phosphorus(V)

alia,

H,P=CF,

binding

(142)

reaction

, structure

of

with

(methylene)phosphorane electrocyclic

for

and

(142)

:CPh*)

metal

a

H,P.CHXY.

contrasts

_c&==p=%yc _ / \

145).

to

calculations

phosphines

I

inter

bind

ether.

model

where for

n = O-3)

that from

or

routes

to P=C

equation rearranges

(21), to

X3can

be

as-phospha-

Equations

which

the

(144)

(20)[2461

and

substituted distances

are

ca.

RP[:C(SiMes121the

phosphirane

12471

Me,Si-C-P(NPr’z)z NZ

___j --N

(Pr’,N),P-C-SiMe, 2

(144) l (Pr’,N),PmC-SiMe,

+-+

(PripN),P’=C--SiMe,

. . . (19)

54 -+ RP[=C(SiMeJ)ZIZ

+ 3(Me,Si),CCl(Li)

RPCl,

+ 3LiCl

, . . (20)

+ Cl,C(SiMe,), R = Me,N.

PhS.

Ph,CH.

EtMeCH

CRZR3 R'P=CRZR"

-+

+ R4,CC1(Li)

//

RI-P

% R' = Bu",

Reaction finally

or Ph

between

BuLi

and

to the fluorinated

(Me,,Si)zC

CR",

Ph or mesityl = Me,Si

R2/R3/RR

. . . (21)

+ LiCl

; /‘\

(Me,N),PF,.(CH,),.PF,O, ylid,

leads

(Me,N)zPF:CH.CHBu.P(NMe,),,

Cl

/ CpzM\CH=P(NMez).,Me,_.,

CPhz

(146)

(145) Cl

I ,CHz\ CP~2r,CH,P(NMe2)2 2

through

(Me,N)ZPFZ.CH2.CH:PF(NMe,)2.

possible including

(Et,N),P=CHSiMe,,

(Me,N),P-CHSiBu',Cl, base

reacts

with

Similar CpzMCl,. with

a chlorosilane,

where

CpzZrC1,

synthesised

phosphonium

transylidation M = Ti,

of new silylated

Me(Et,N),P=CHSiMe,,

has been

on the silylated

(Me,N),PF:CH.CH:PF(NMe,),

A range

intermediates.[2481

such

reactions

salts

Zr or Hf. gave

and Me(Me,N),P=CH,

(Me,N),P=CHSiMe,,

by the action obtained

as Me,SiCl between

as

ylids,

when

of a strong

R,R',_,P=CH,

and Bu',SiClp.[2491

Me,_,(Me,N),P=CH,

the complexes

the product

was an

(146).

and though

isomeric

form

(147). [2501 Gold atoms

in square is found

planar

coordination

in the dihydrated

to two chlorine

complex

(m),

with

and two carbon the eight

55 membered

ring

adopting

the

chair

conformation

In the

[2511

stable

Cl* CH,-Au-CH,\

/ PhzP\

PPh, /

CH,-Au-CHz Cl,

copper(I)

chloride

coordination 211.3

to

and

with

chlorine

190.6pm

a P-C-P

angles

complex

and

Ph,P=C=PPh,

the

ylidic

of

from

123.8”

the

carbon

respectively.[2521

angle

result

with

metal atom

is at

differences

the

in

difference

the

in

linear

distances

The PCPCu system

and

in is

of

planar

the

two

P-C-Cu

of

the

two

conformations

Ph,P

groups. Tetraphenylphosphonium the

bromide,

and

C-P-C

The form

has angles

distances

between

Related

ligands

these

can

and

with

via

the

Mo(C016,

of

dihydrogen

lithium

to

Bonds

to

Silicon

Li,PH

are

linear

acyclic

such

four-membered structure

all

with

been

n = 2

synthesised

abstraction for

an extensively

as

products

to

in

the

ammonium

and

hydrogen

determination

reacts

bonded

but

in

and

is

case

which

compounds

used

in

together

material

in of

spectroscopy of

(1521

place with

(ClEt,Sil,PH

formation

N.m. r. the

cyclic

(HP.SiEt,l,,,,,.

starting

(155).

the

Et,SiCl,

Et,Si(PH,l,. as

LiPH,

among

Me,Si(PH,),, and

If are

with

silylphosphines.

Me,Si(PH,)Cl,

PH, evolution

heterocycle

of

(H,P.SiMe,),PH

But,SiC12 leads

LiPH,

also

Structures

a series

Et,Si(PH,lCl,

(H,P.SiEtZlzPH. with

n = O-2

complex

diphosphonates,

(~1-(1541.[2571

major

species,

have

show

give and

the

Me,SiCl,,

to

products, and

with 179.3pm

atom.12541

Dimethyldichlorosilane

Atoms.

PH.SiMe,Cl

(HP.SiMe,ls

and

network.[2561

mixtures

H=P.SiMe,.

the

by proton

methoxide.12551

(M+1~[(HO1O(O)P.CH,P(OlO(OH)1Z-

and

in

phosphorus

anions

methylene

dimensional

isostructural 178.1 for

and

phosphine

converted

thallium

not

111.6”.[253]

[Ph,P(0)I,[Ph,P(S)13-,CH be

presence

three

is

between

Ph,P[P(Ol(OEtl,l,_,

complexes occurs

which ranging

108.1

phosphoryl-phosphines Mo(CO),L

coordination and

chloride,

P-C

of the

and

the

reaction

the was

an X-ray

used

for

56 structure with

determination

close

to C,,

six-membered Reaction

symmetry

rings,

has boat-boat

implying

group

silylphosphine

H

and

that

The molecule

conformations

it is a precursor with

formation

is bonded

H

f

(152)

leads

of a new Cr(C0J4

of

for the two (Me,Si),P,.

to displacement complex

via the two PH phosphorus

where

atoms.

P-H

Me,

I

P-P

/

performed.[2581

of Cr(CO),(norbornadiene)

of the organic the

was also

P-H

\

Me,Si \p/siMez

P -SiMe,

;1

-SiMe, Me,Si MezSi

(149)

(151)

(150)

Me,

/c\ P

\

Me,Si

I/

Si

Si

Me,

SiMe,

Me, \I

P

P

H'

'H (153)

(152)

Me,

/=\ Hp\sl P

‘P

Li

But>

Buts?

’

/

7\

PH

“‘\

Si

. /ps1Me2c1

But*

But*

(155)

(156)

Li (154)

ClMe

P-SiMe

-Pi"\ =

Si

\

/,, Si

But=

But2

But2

(157)

(158)

Me,

/=\ ClMe,Si-P,

,P-SiMe,Cl

Si Me, (158)

Compound

(255)

mono-lithiated DME.12591

(160)

can be lithiated

with

product

as an adduct

Treatment

isolated with

Me,SiCl,

either

then

LiPH,

or BuLi

with

leads

and

two mols

the

of

to mixtures

of

(m)-(m). The major compound reacted separated

product

(159). species

when

but a small (160)

quantity

is also

and on attempted

adamantane-like

in the absence

maximum

amount

Silyl

while

MeP(S)(SSiMe,),

and P(S)(SSiMe,),

products

of these

Me,P(S)P(S)Me,. intermediates with

Me,PSiMe,

intermediates

MeP(SiMe,),

partially

The mixture

phosphines to give

thus

will

with

with

the

Me,PSiMe,

are

carried

(Me,SiIzS.

such as Me,P.SSiMe,,

out

are MeP(SSiMe,)(SiMe3)

P,Me4

The by-

and

in pentane

With

gives

give

and Me,P(S)PMe,

material.

be

to the

react

respectively.[2611

reactions

cannot

leads

products

and P(SiMe,),

Reactions

as the starting

is the bicyclic

thermolysis

incorporation:

Me,P(S).SSiMe,.

Li,P

of a monocyclic,

formed.[260]

of a solvent

of sulphur

with

distillation,

P 4. (SiMe 2 ) fi

sulphur

reacts

Me,SiCl,

are

slower

but

can be observed

MeP(SiMe,),,

and MeP(SSiMe,),

the

and with

58

P(SiMe,l,.

the three

2. are all

observed.

reacts

with

to give

at temperatures

(Me,SiSl,P(Sl

Silylated obtained

was

diphosphines

by treating

R'P(SiMe,lLi

stable

with

ButPC1,

as

low as 20°C

gives

from

R(Me,SilP.PCl,, with

(R' = But or Me,Sil which

n = 0 -

the decomposition and

sulphur.

for R = Me or But,

PCl,,

are

and on treatment

are unstable with

for example

the cis-form

only

n = 0 -

sulphur

where

(Me,Sil,P,

can be converted

of chlorine

products,

with

ratio,

P,(SiMe,),(SSiMe,),.,

RP(SiMe,),

Substitution

more

on the reaction

isolated

Bu'(Me,SilP.PCl.P(SiMe,)R'. [2621

P(SiMe,l,(SSiMe,l,_,

Depending

P,(SiMe,l,

3, but even product

compounds.

either

with

to triphosphines

at room

temperature.

Bu' or Me,Si

leads

to

(Me,SilzP.P(SiMe,).P(SiMeslBuk

of the cyclotetraphosphine

(=1.[263

But-P-P-SiMe,

But-P-

’ cl-

P-SiMe,

(161)

salts,

[Ph,P(CH 24z3 C H Ol,lBr

produced

when

(162)

where

reacts

Reduction

furfurylphosphines,

[RP(CH,C,H,O),lBr,

which

RP(SiMe,),,

with

lithium

are potential

Tetramethylpiperidino-substituted

reaction

stable with

0

R = Me, Et, But.

with

Ph,P(SiMe,1.[2641

thermally

CH z Br

(162)

Furfuryl-phosphonium and

\

products

formulated

Me

Me

Me

P(SiMe,), aluminium

bi- and

as

(163.

product,

Pr',N.PClSi(SiMe,l,

rearranges

give

X = F or Cl) on

lithium.

but the

(164)

exchange

ligands.

dihalides

XPSi(SiMe,l,

chlorine-Me&i

gives

related

P-SiMe,

(163)

are

or hydride

tridentate

phosphorus(III1

tris(trimethylsilyllsilyl

Me

[P(CH,C,H,O),lBr Ph or mesityl.

on heating

via

to Pr' 2N.P(SiMe,l.SiC1(SiMe,),.[2651

59

The first five-coordinate P(V)-Si compound (164) has been synthesised by treating tris(catechyl)chlorophosphorane (C,H,O,),PCl with the novel silylating agent Mg(SiMe,l,.DME

in

pentane at -28%.[2661 Bonds to Germanium.

Butene is lost when the phosphagermene

(mesityl),Ce=P(C,HzBut, ) is heated in benzene at 160°C forming the first stable germaphosphetane

(=I.[2671

(mesityl),Ce-PH

But (165)

5.2.4

Bonds to Halogens

The +3 Oxidation State.

The phosphorus analogue of NOF has

recently been prepared by treating P(O)FBr, with silver in the gas phase at 1lOOK and 10m2 mbar.12681 isolation spectroscopy

Mass spectrometry and matrix

(v,_, 1292.2 cm-' and vp_p 811.4 cm-l)

confirm the identification.

An alternative route to POCl is the

pyrolysis of ally1 dichlorophosphite

(CHZ:CH.CHzOPC1,) at 1150K in

which ally1 chloride is lost; again the unstable species was identified by mass spectrometry and Ar matrix i.r. spectroscopy. Finally high temperature gas phase hydrolysis of PCl, and 16911 PBr, lead to POCl and POBr respectively which can be stabilised in argon matrices.[2701 An alternative to the normal inversion prqcess (via a planar intermediate) for three coordinate Croup 5 compounds has been proposed in which there is edge rather than vertex displacement leading to a T-shaped intermediate.[271.272,2731 alternative

This

is considered to be particularly important for

compounds carrying electronegative substituents and is supported by m.0. calculations showing stabilisation of the T-shaped over the planar intermediate by 35.6 and 56.2 kcal.mol-l for PHF, and PF, respectively. Substituted aryl difluorophosphines 2-MeOC,H4PF, and 2-Me=NC,H_,PF, have been synthesised, and although the former is

60 stable

it disproportionates

at -3O"C,

and

to Z-MeOC,H,PF4.

the highly

at room temperature

puckered

or above

cyclotetraphosphine

[Z-MeOC,H4P1,.[2741 Dithiols give

and

diols

(n = 3-6).[2751 species

Cyclisation or AsF,

reacts giving

M = Pl gives

Me,Si-

1 gand

invest

with

I

behaviour

loss of two mols

phosphorus

Me,Si-0

F,PSH

molybdenum

when

and

carbonyl

either

PF,

Li,[OSiBu',OSiMezOSiHydrolysis

acid

ester

of

(166,

(1671.

Me

-SiButz

I

I

I I

I

O-M-F

Bu',Si-0

Although

other

phosphorus(III1

products

Phosphorus,

substituted

M = P, As or Sbl,

with

210.0/213.0pm

M-N

represented

chlorides

PhC(:NMel (NMeCll for which

are discussed.

distances

X-ray

arsenic

between

with

the

, . (221

+ Pz&,

cyclic

n.m.r.

of

(221.[2771

react

to give

detailed

of 180.7/181.0,

for phosphorus,

reaction

in the presence

by equation

-+ 3[BHI[PS,C 11 + 15BHCl

+ 18B

data

the overall sulphide

and antimony(III1

benzamidine

spectrometric

and hydrogen

(Bl is best

arsenic

+ 9H,S

are formed,

chloride

2-methylpyridine

similar

rlre

-P(OlH

(167)

(1661

(168,

salt,

0

But2Si-

7PC1,

toward

(166, M = P or AsI.12761 the stable

eliminate

and FzPO.(CH,l,.OPF,

of LiF occurs

the trisiloxane

with

S(PF,l,

(n = Z-61

gated.

0 -SiBu",

0

with

CH,),.SPF,

The

has been

Bu",Ol

on reaction

F,PS.

respectively

products

and mass

structures

are

195.4/194.3,

and antimony

very and

respectively.

[2781 Continued

interest

investigation

PCl,

in phosphenium

of the reaction

+ 3P(NMe,l,

+ 2AlCle

salts

in equation

has

led to an

(231.[2791

--t [(MeZN1ePC1l[AIC1,l

+ [(Me,Nl,P:P.P(NMe,l,l~AlCl~l

phosphine

product

rapidly

The tri-

adds

one mol

of AlCl,

. ..(231

at the central

6 phosphorus

and

a

small

amount

of

[(MezN1,P.PH.P(NMe,l,IIAIC1,l, presumably all

from

trans

the of

If

MePCl=

isolated.

is solvent.

isomer

a

the

second

product

formed

During

by

the

addition

course

cycle-tetraphosphine is

treated

with

of

of

(1691 glycol

in

HCl.

this was

work,

the

also

dichloromethane

Me-P
2 CH z Cl

I

CH, \

b

LMe,

\

Me-P
(169) without

a

reaction and

tertiary

amine

course

is

as

altered

a

hydrogen

giving

chloride

[MePH,ICl

acceptor, (structure

the determined)

(1701.[2801

Iodine(V) 0°C of

(170)

to,

fluoride

elemental

etc.

can

hexachloroethane

or

R3_,PH,

+ n&Cl,

RR’PH

Direct

+ n&Cl4

-$

treatment

nHC1

and

or

on

and

with

phosphines,

treatment

R,PCl.

+ 2S0,

HCl

+ SOCl,

+ SO,

primary sulphuryl

and

RPCl,

liberation

with

R,P(OlCl

either and

ary11.[2821

. . . (241

+ R,-,PCl,

+ SOCl,

of

RzPCl

RPF,

secondary

RPCl,.

2HCl

with

R,PF, and

(241, to

-+

oxychlorination on

directly cycloalkyl

+ 2SO,Cl,

possible

primary

equation

R = alkyl,

+

+ 3SO,Cl,

PCl,

R,P, R,PF,

R,PF,. and

e.g.

converted,

(where

oxidises

R,PF,,

iodine,[2811 be

R,P(S)H

RPHz

rapidly

respectively,

+ RP(OlC1,

. . . (251

+ RR’P(O)Cl

secondary chloride,

. . . (261

phosphines equations

is

also

(251

and

(261. Metathesis

between

dihalogenophosphines

AgSCN

and

mono-substituted

gives

RP(NCSlz

where

R = Me,

Et,

Ph

or

C6F5,

at

62 there

is evidence

spectroscopy

for the

and bonding

room

of secondary

characterised

diphosphine, compounds and

RR'PPRR'.

obtained

by

n.m.r.

i.r. unstable

at

RR'PCl.

as products

and either

were

those

Ph,PCl

with

has been

of reactions

prepared

between

or PhPClz;

among

a

the

R = R' = Me, Et, Pr, BU or Bu".

R = Me or Ph: R' = Et, Pr or Bu.t2841

Nitrogen

trichloride

can oxidise

R,P where

elimination

of nitrogen

leads

The

to mixtures

and

PO,Cl,

either

routes

POCl,

(space and

out

group

strong

P6,/mmc)

157.7/153.4

Trigonal

data Bond

axial

distances, P-Cl

effect

bipyramidal values

by

with

geometry less than

conjunction

with

force

fluorine

matrix

constants.

1. show an

angles

data

diffraction

where

n = l-4.[2881

increase

content,

Deviations

Raman

isolation

values

preferentially

by electron

1" for equatorial-axial angles.

of 158.0

electron

chlorine

with

distances

respectively

PCl,F,_,

bonds.

are small

of PF, has

gas phase

indicated

in Table

study

D,, symmetry

with

with

increasing

between

spectroscopy.

fluorides

at the axial

equatorial-equatorial

valence

are

chloride

summarised

distances

greatest

has exact

from

135"

of silver.

crystallographic

be compared

structures

positions

reactions

and equatorial

158.1/153.4pm

matrix

of ca.

Alternative

temperature

vibrational-rotational

for the mixed

angle

in the presence

axial

cloramine

in an argon

bond.[286]

should

with

with

(NPC1,)3,,d,.t2851

of POCl

the molecule

with

bipyramidal

occupying

and tertiary

of PCl,

has an O-P-O

are high

an X-ray

These

and

and

P-Cl

and oxygen that

showing

152.2pm.L2871

diffraction

i.r. data

to PO,Cl

or PCl,

carried

to PCl,

reaction

Ozonolysis

from

It is interesting been

but the

State.

which

an unexpectedly

preparative

PCl,

R = Me, Et, Bu or Ph, to R,PCl,

of the cyclophosphazenes

+5 Oxidation

gives

and

is suggested

are all thermally

chlorophosphines.

by n.m.r.

phosphines.

of

compounds

from SIP

temperature.

A series and

RPX(NCS)

via nitrogen

The

spectroscopy.[2831

intermediate

from

deviating

in both

trigonal from

the

ideal

and ca. 2" for for the compounds

i.r. data were

used

P-F

and the

in

to obtain

63 Table

1.

Bond

distances

PF,

and

angles

PClF,

PCl,F,

for

PC1,Fs_,

where

PCl,F,

PC1,F

n = O-5.

PC15

P-F,

1.534(41

1.535(3)

1.538(7)

P-F,

1.577(5)

1.581(4)

1.593(4)

1.596(Z)

1.597(4)

2.000(3)

2.002(31

2.005(3)

2.011(31

2.023(3)

2.107(61‘

2.127(31

P-Cl, P-Cl, X,PX,

120”

117.8(71”

121.8(41b

120’=

120.0(l)b

120b

X,PY,

90”

90.3(4)=

90.0(31”

90d

90.9(2)”

90’

“F,PF,.

bC1,PC1,.

Reactions of

between

compound

(172)

while

mols

‘F,PF,.

RPF,

Methods

lead

Spiro

compounds

for

to

preparing

(PClsl,(PCl,)(C1).

= F,

Me,

Ph

monocyclic

chlorides

salts.

have

recently

from

heating

or

adamantyl)

and

one

mol

benzoxazaphospholes

(1731

are

the

phase

III

modification

The

yellow

but

there

been

products

with

two

iodine solid

are

TiCI

is

isostructural

either

of

and

POCl,

contains

chloride a

secondary

Raman

and

double

with

involves or

the

excess

amine

shifts

salt, PCI,

in

with leads

the

other

and

12921 results

either

POCI,

tin

with planar at

PFSs-amine

or

analogue. a mixture

alkylammonium to

of the

which

treating

PCl,’

i.e.

(PCl,l(ICl,)

P-Cl... I interactions

treated

PCl,.

Two

dichloromethane

tetrahedral

two secondary

Phosphorus(V)

The

of

preparation in

and

of

discussed.12901 [2911

synthesised.

solution,

the presence

reviewed bromides

(PCl,),(TiCl,)(PCl,l

tetrachloroiodate and

been and

a mixture

nitromethane

PCl,

the

have

phosphorus(V)

The

(R

(1711

“Cl..PCl,.

the aminophenol.[2891

of

(PCl,)’

dC1,PF,.

of

chlorine. ICl,-

354

and

fluorides adducts,

ions 379pm. in

64 equation

3PC1,

rather

(27).

+ SEt,N(HF),

than

PF&

+ 13Et,NH

salts.[2931

The products

.+ 3PF,.HNEt,

give

+ 5Et,NHCl

. . (271

+ lOEt,NH,Cl

salts

of the

salts

with

N.m.r. [PCl,l

(ROPF,).

primary

data

when

treatment

ion with

aromatic

point

to the formation

phenol

reacts

of catechyl

aminolphosphine

and

PCl,

with

and phenol

and

of (PhO),PCl

phosphorus

phosphorus

follows

[R'RZP(NMe,),lC1

ethanol

(ArNHPF,l-

amines.

equation

trichloride

+ P(NMe,l,

with

(281.12951

[RIR~P(NMe,lC1lC1

or

[(PhO),Pl-

pentachloride.[2941

triscdimethyl-

The salts

are produced

in the

O\P(NMe,),

-+

and

+ cl-

0'

. (281

+ Cl,PNMe,

oxidation NMe,

of.

respectively,

or Cl) with

oxidation

leads

with

PBr,

(174)

halide

= OPh,

with

PCI,

itself

(Me,Sil,O

reaction

of POCl,

with

THF

P(O)Cl,_,[O(CH,),Cll,,

is P~P(O)[O(CH,),Brl),

gives

investigated

with

catalysed

in the series

reaction

Recently

Me,NCl;

(RI/R2

ICl,P(NMe,l,lPC1,.[2961

the product

catalysed

and R1R2PC1

N-chlorodimethylamine, to

The mercury(I1) to compounds

R'R2P(NMe,)

and

only

but with

PCl,[O(CH,),Cll.

reactions

where

leads

n = 1-3;

PCl,

the

[2971

of l-oxo-1-chlorophospholene

(Me,Sil,NH

are summarised

A3

in Scheme

3.

[2981 The

chlorine

stepwise

atoms

fashion

in Cl,P:N.P(O)Cl,

by trifluoroethanol

(CF,CH,O)PCl,:N.P(O)Cl~,

a diphosphorylimide,

Two

new six-coordinate

[MeP(CN),I-. an excess

result

of silver

of phosphorus(V) considers general

from

solvolysis

on further

halides

takes

and

reaction

the

last compound

(CF,CH,O),P(Ol.NH.P(O)(OCH,CF,).[299l phosphorus(V) treatment

of

cyanide.[300]

the behaviour

in a

to give:

(CF,CH,O1,PCl:N.POCl,

(CF,CH,O),P:N.P(Ol(OCH,CF,),: gives

can be substituted

with

[PhPCl,(CN),I-

[RPCl,l-

A further

100% sulphuric

of a range place

anions,

(R = Me or Ph) with report

acid

of methylated

which

is faster

and

on the study

and 25% oleum species.[3011

for bromides

than

In

65

//O \ Cl

0 I

(Me,Si),NH

//O

low temp.

I

'\

>c

NHSiMe,

(174)

(Me&Si),NH

//O

100°C

I

p\

'C

Scheme

chlorides oleum

and

there

standing

MeP(OH)ClBr+,

Bonds

The

in this

and within

treated

mols

for,

MePClBr,'.

and MePBr,'

and after

assigned

MePBr,

inter alia.

in

long

to MeP(OH),+.

MeP(OH)Br,'

section

is initially

the two sections,

and

State.

multiple

Treatment

of Bu*,&H,NHLi

two coordinate 157.3

evidence

With

The

MePCl,',

and MePBr,'.

in terms bonds

of oxidation

to nitrogen

are

first.

+3 Oxidation

three

signal

in oleum.

to Nitrogen

Sub-division state,

show

3

than

for MeP(OH)Br,'

is a 31P n.m.r.

reactions

MePCl,Br+,

in 100% H&SO,

is evidence

there

MePBr&l=

5.2.5

faster

+

OSiMe,

imides,

163.3pm

at phosphorus

(As-N

(98.8"

of MCl,,

in ether

gives

Bu",C,H,NH-M=NC,H=Bu"J 171.4 and

174.5pm)

at arsenic).[3021

M = P or As, with

the novel, with

isostructural,

P-N distances

and an angle

The two aryl

of

103.8"

groups

are

of

66 magnetically but

there

distinct

is a slow

equilibrium -P=P

and

-P=S

important

shift

proton

in equation

silylphosphides An

up to at least 400K

units

have

M(=NAr)(NHAr)

G

RP(SiMe,Bu*)Li

been

obtained

to n.m.r.

indicating

from

the double

data

the

containing

-P=N-,

reactions

see equations

chlorides,

in introducing

in intermediates

in C,D,

Compounds

(29).

and acid

step

exchange

according

between

(30)-(32).[3031

bond

is a 1,3-silyl

of the type RP(SiMe,R)(X=O).

M(NHAr)(=NAr)

+ NOCl

-b LiCl

RP(SiMe,)Li

+ Bu',P(O)Cl

RP(SiMe,)Li

+ (mesityl)S(O)Cl

(29)

. . . (30)

+ RP=NOSiMe,Bu'

-) LiCl

. . . (31)

+ RP=PBu',(OSiHe,)

.-) LiCl

+ RP=S(mesityl)(OSiMe,)

. . . (32) R = But 362 C H

An

iminophosphine-iminophosphorane

diazadiphosphetidine transient probably below

an

favour

(177)

intermediate.[304] above

reactions

as

is treated

diazadiphosphetine

-40°C

reported such

(176)

(E),

which point

form

with

formed

Compound

it dimerises to the

is obtained carbon

when

the

tetrachloride;

by loss of Me,SiCCi, (175)

to (178):

instability

as the equilibrium

of the open

(175)

is in fact, these

a is

stable

on1

and other

of diazadiphosphetines

is extensively

displaced

in

isomer.

SiMe, NPr',

I C l-P-N=P(NPr',)

II NSiMe,

(175)

/N\ Pr' zN-P,N,P-NPri,

Pr'zNip Cl'

//N\P_NPr, =

\N/

I

I

SiMe,

SiMe,

(176)

(177)

67

Pr’,N

NPr’,

I I

I /P’N-P-Cl

Cl-P-N II

‘P

II

’

Me,SiN

NSiMe,

I

NPr’,

(178)

(179)

(180)

Trimethylchlorosilane substituted giving polar

(180)) P-N

piperidine

is

eliminated

piperidino-phosphorus which

double

contains

nitrogen,

be

expected.

occur

in

the

The

on the

a mixture (179)

an unusually

bond.[3051

would

from

dichloride

other

long

formal hand,

(160pm)

single is

bond

shorter

Phosphorus(IIIl-nitrogen

triazaphosphapentalene

dicyano-diazaphospholes

(1821

obtained

secondary

the LiN(SiMe,l, and

to

highly

the

(166pm)

double

(181) with

of and

bonds

than also

by treating

alkylamines.[3061

CN P CN H

NRz (181) Ligand complex,

exchange

(182) between

CpMn(COl,(octene)

(Me,Si12N-P=NSiMe, gives

an

intermediate

and

the which

cis-octene treated

with

68 Re(CO),Br bimetallic

loses

carbon

complex

monoxide

and Me,SiBr The

(183).[3071

and gives

the unusual

same amino-iminophosphine

SiMe, ZjiMe, /N\ CpMn(COl=P,N,Re(COI.

(Me,Si),N,+

p,N\p//N-SiMe, ..

_

SiMe,

(184)

(183)

with

Fe,(CO),,

(184)

containing also

is converted

stabilised

to a tridentate,

as a [Fe(COIJlz

coordinated

cluster:

(Me,Si),NP

six electron

a second

donor

species

and Me,SiOP=NSiMe,

groups

was

isolated.[3081 phosphenium

In general,

cations,

[(Pr' ,N)PCll‘,

give

treatment

with

1,3-dienes,[3091

phospholenium

converted

in a one

step

[(R,N),PI+ cations

while

process

(R = Me or Pr'l such as

(185)

the related

on reaction

with

and

on

[(Me,N)PCll+

is

cycle-octatetraene

\// 4a

c1 A ; ’ NMez

to the 9-phosphabarbaralane Both

MeN(PF,l,

RN(POF,l, as Me,SiOMe

by N,O,

and EtN(PF,l,

are oxidised

in hexane,[3111

and Me,SiNEt,.

difluorophosphoric

(~).[3101

acid

cleave

in good

but silylated the P-N-P

derivatives

as shown

yields

to

nucleophiles

bridge

such

giving

in equations

(33) and

(34).[3121

EtN(POF=),

+ Me,SiOMe

EtN(POFz),

+ Me,SiNEt,

--t F,P(O)OMe

-t F2P(0)NEt,

+ F,P(O)NEt(SiMe,)

+ FzP(OINEt(SiMe,l

. ..(33)

. ..(341

69

PhN(PCl,l,

has

phosphorus

lone

arrangement is

a CZV conformation pairs

with

consistent

with

have

course

of

low of

been

the

(equations

to

reaction

solid

169pm and 3’P

from of

+

lZPhNH&l

with The

with

angle

series, to

and

unravel

phosphorus(III1 reaction

’

110.8”

(1871

designed

the

chloride

now appears

to

Ph

_;h_p,i\p,NHph

p,i,p PhHN’

of

data.

Ph

+

the

This

a P-N-P

n.m.r.

experiments

aniline

(3611.[3141

state

group.[3131

diazadiphosphetidine

and

19PhNH2 + 4PC1,

of

the

phenyl

temperature

the

isolated

(351

in

the

P-N distances

Two new members (-1,

trans

‘N’

N’

;h

;h

. . . (35) (1871

PhHN 5PhNHz + 3PC13

+

9PhNH&l

+

Yh ,p,N\p_;h_p/NHPh \

‘N’

NHPh

Ph

. . . (361 (1881 depend

critically

involves

the

on the stepwise

[(PhNHlPNPhJ, Reaction leads

to

and of

trans

or

isomerises

amino

groups

in

etc.,

can

o-styryl,

treatment

form which

[(CP,CH,OlPNPhl,, The

(1881

with

R,PX:

reactions

i&O,.

HzO,

the

LiAlH4

of

route

of

the

were

and the

the

also

and

triethylamine

product

solution

slowly

but

almost

cis-form.[3151 and

replaced

amine

in

and

(1871.

trifluoroethanol

RP(NEt,l, be

conditions

[(PhNHl,Pl,NPh,

dinuclear

substitution

on standing to

exact

(Ph2NHlsP.

to

with

appropriate the

of

en

cis-[CIPNPhla

the

completely,

stoichiometry

formation

R=PNEt,, by chlorine

hydrogen derivative reported.[3161

halide with

for

R = vinyl, or

bromine

to

give

other

ally1 on

RPXz and

reagents

such

as

70 Although reaction complex

a mono-substituted with

Na,Fe(CO),

in ether

(189)

containing

a P(NEt,),

On decarbonylation

rings.[3171 the

original

Fe-Fe

bridging

and Fe-P

Et,NPCl,,

species, below

are formed

group

to give

the product

and both

in solution

diethylcarbamoyl

bonds

0°C.

group

was used

in the is a

FeP,

and FeOPC

at room

temperature,

becomes

terminal,

new

(190).

Et,N \

c-o

(CO),

I

I

(OC),Fe-

(OC)fe /_

P-Fe(CO),

I

I

Fe -

I

Et,N -P -P

\

/

Et,N-P \

'1

Fe(CO),

I NEt,

I NEt,

(189)

Sulphur

P-C(O)NEt,

(190)

tetrafluoride

(Et,N),P.CiC.P(NEt,),

will

oxidise

the substituted

and the corresponding which

Co,(CO),.L

in a room temperature

(191)

obtained The

chlorine

behave

morpholine

to F,(R,N),P.CiC.P(NR,)F,

co,(co),.[31B1

Fe(CO),

atoms

as ligands

acetylenes, products,

in the complex

reaction

with

in fat-[Mo(CO),(PCl,),l

C

can

PF,(NR,),

~OC~,Co' / I / (OC),Co Llll C-PF,(NR,),

(191)

be substituted has C, point

by Pr',NH, symmetry

Borylaminophosphines, containing

(Me,Si),CH

(Me,Si),N-BBu'(NHLi)

X/Y = MezN,

to give

fat-(Mo(CO),[P(NHPr')~J~I

and P-N distances see equation groups

+ ClPXY

Ph. Cl, PhlCl,

(37),[3201

13211 have

-t LiCl

which

of 167pm.[3191

been

and aminophosphines

synthesised,

the

+ (Me,Si)2N-BBu'(NHPXY)

N(SiMe,),/Cl,

etc.,

. . . (37)

71

latter

involves

successive

(Me,Si),CHMgCl obtained

are

or

and

latter

group

a variety

where

where

on the decomposition

or PhPCl,

R = SiMeJ

and R, =

and

react with

which

depend

of

route

the

with

the compounds

R = H. Me, Ph, CH,SiMe,

of compounds

of products

PCl,

Among

(SiMeJ)(SiMe,But),

(Me,Si),CHPRN(SiMe,),.

give

of either

silylamide.

(Me,Si),CHPCl(NR,),

SiMe2.CH,.CH,.SiMeZ

The

treatment

and a lithium

carbon

or CH:CH*.

tetrachloride

on the nature

to

of the R group

intermediate

[(MeJSi),CHPR(C1)N(SiMe~~~l[CCl~l. Reactions

between

products

RPClCH,PClR.

for R = Cl, Pr' or Bu'.

and

and phthalohydrazide

yield

N,N'-dimethylhydrazine,

hydrazine.

such

as

(192, R = Cl, Pr' or But,

The

(~I.[3221

structure

of

R' = H or Me) and

(192. R = But.

R' = H) has been

Me

R\p/\p/R \ I N-N / R' 'R'

Me \ N";

/ PAP

(192)

Me

jN -

N\ Me

(193)

Symmetrically

determined. But,M.NSN.MBut2 to give

potassium

phosphorus

salt

salts with

K[NSNMBut21,

Bu',AsCl

The

at the phosphorus

+5 Oxidation

azides

have

transient

>PzN

phosphazenes azides and

discussed

species

(R' = Bu*,

R' = CH(SiMe,),,

subsequent

to be formed

via a 1,3-silyl

phosphorus(V)

species,

depends

amide

of the

a chalcogen

reaction

is

this

of phosphorus

for the formation Although

to a three

on the specific

the new RZ = NPr',;

are decomposed,

is dimerisation,

migration

when

R' = NMe,,

or N(SiMe,),)

of

such monomeric

initially

R2 = Bu' or NPrlZ;

rearrangement

potassium

derivative

and pyrolysis

and evidence

whether

diimides, with

atom.

R2 = NC,HJMe4

behaviour,

with

reviewed.13241

are considered

R'RZPN,

a mixed

Thermolysis

State.

been

sulphur

and treatment

gives

On treatment

Bu',P.NSN.AsBut2.[3231 specifically

substituted

M = P or As. are cleaved

where

trimerisation coordination

substituents.13251

or

72 Primary CH,Ph

RNH,

amines.

react

or cyclohexyl,

PhP(S)(NHR),

mononuclear,

1

PhP(S).NR.PPh(S)NR, ively

R = Me, Et, Pr, Pr',

in non-polar

form

solvents

and dinuclear,

and

Bu, Bu', to give

Bu",

both

is favoured

latter with

is formed

exclus-

low stoichiometric

of amine.

Phenoxy-substituted esters

react

phosphoryl-phosphazenes

with

PCls

according

respectively.[3271

N-silyl

(PhO),P:N.P(O)(OPh),

+ 2PCl5

and

phosphinimines,

-'

imidodiphosphoric

to equations

(38) and

R,P=NSiMe,

(PhO),P(O).NH.P(O)(OPh),

[(PhO),P:N.P(OPh)~Cll'[PC1,1-

. . . (38)

+ 3PC1,

+

[(PhO),ClP:N.P(OPh)&l~-[PClGl-

or Me, R, = Bu'NHIPh,)

react

(Me,P:N),WF,.[3281

The

of

and a N-W-N

181.6 The

and

182.3pm

recently

and

172.8pm

conjugation

former

with

to give

[(Bu"NH)(Ph,P:N)I,WF,

is the cis angle

WF,

. ..(39)

form with

W-N

and

distances

of 99.6".

sulphinyliminophosphorane

shows

P=N,

respectively,

S-N and C-S distances

confirming

the absence

of

156.6,

of

in the system.[3291

Structures hydrazine

latter

synthesised

Ph,P:N.S.C,H,(NO,),-2,4 166.0

+ 2POC1z, + HC1

[(4-MeC r5BJ H ) P:Nl,WF,,

(4-Me&H,),P:NWF,,

(39)

(R =

+ POCl,

4-MeC,H4

Bu",

cyclophosphazane

The

products.13261

in the trans

quantities

acid

where

have

products

also

been

is centrosymmetric 0

determined

(194)[3301

and

with

for two phosphorus(V)-

(195)[3311.

all three

rings

O+

OPh

The in chair

conforma-

,NMe,

\\/ HNiP\NH Me/d

kMe

'P' PhO/'\O

PhO'

(195)

(194)

tions,

while

reacting with

the

latter,

(PhO)P(S)(NMeNH,),

a twist

ring

Transilylation

+S

a potential with

antitumour

(Me,N)P(O)Cl,,

agent

obtained

is the 2 isomer

conformation. with

RMe,SiCl,

for R = Ph, CH:CH,.

CH,Cl,

by

73 CH,CH,CH,CN, into

etc.,

converts

the

RMe,SiN=P(OCH,CF,)Me,

either

while

Me,Si[N=P(OCH,CF,)Me,1,

depending

on the

reaction the

(196)

together

with

According

13331

the or

product

is

the

31P n.m.r.

with

data,

Me,SiNH

I +PPh,

Lp

(197)

amine,

OH

‘N/

‘NHSiMe

reaction

are

obtained

py.PS,Cl

with

PSCl 3 and hexamethyldisilazane.

from

and benzylamine

gives

the

into

methyl

in the

triethylammmonium (198).

crystallisation iodide

which cis

then

presence salt

of

and trans gives

the

dimethyl

forms.[3351 ester

(199).

(199) reactions

between

R’O,

R,PP,_,.

(CH20)2.

XC6 H4N9 where

X = H, Me, Cl,

wide

di-

where

n = 1 or

and substituted

Br or

NO,.

have

been

and tetrafluorodiazadiphosphetidines,

and fluorinated

Substituent

by

$H,Ph

O(CH,)sN, of

triethyl-

a new tetra-

isomeric

(198) Staudinger

of

can be separated

$H,Ph

range

3

SiMe,

thiodiazadiphosphetidine

(40),

ring

(197)

With

(CH,),N,

and the

N-Ph

[3341

Treatment

as by-products.

/N\p//S

HZ

fractional

in

heterocycle

Me,SiNHP(S)Cl,

I

B -

compound

PhNH.PPh,:NPh

H, and Me&

PhNH.PPh,.BH,.

N-Ph

I Ph,P+

I

is

$iMe,

B -

Ph-N -

Me,SiCl,

eight-membered

HZ Ph-N -

using

Me,SiCl[N=P(OCH,CF,)Me,l

reacts

product

to

Me,SiN=P(OCH,CF,)Me,

stoichiometry.[3321

When borine-dimethylsulphide dichloromethane,

phosphazene

influence

monophosphazenes, on the

nature

of

equation the

product

phenyl used

2,

R = R’,N,

a-rides, to

prepare

a

equation (41).[3361 and full

‘-F

and

74 31P

n.m.r.

results

are discussed.[3371

6 R z3 -+ %(RPF,NC,H,X)z RR=, + XCHN RR'PF

+ XC,H,N,

A normal (200)

and

the novel

MeN

-+ RR'PF=NC,H,X

Staudinger

reaction

triphenylphosph

+ N,

\

c\/

<

C'

P\

MeN

. . (41)

+ N,

between

ine gives

X'i-PN-X"-P unit . [3381

/

. . . (40)

the azido-phosphorane

compound

(201) containing

A noticeable

NMe

feature

MeNHC\ \

/NMe - N=PPh,

N, NMe

of the

MeN'P

\

NMe

\C'

b’

::

(200)

(201)

0 II

IC\

MeN

\

\

p\NM,/c=o 1

o=CYN~p/o\

'P-C MeN ’

’

\

NMe

MeN

NMe

1

MeN /C\NMe /

’

NMe

’

\C' :

structure

of

(158.9pm); and

(201)

the other

178.5/180.1

distances atom.

is the shortness

and

P-N

respectively Continuing

distances

168.1/168.7pm

I-oxobis(spirophosphorane)

are

of urea

elimination

154.9

five

bond

and equatorial

coordinate

phosphorus

substituted

of Me,SiCl

was expected

bond

for the double

for the axial

at the central

in the area

phosphorus(V)compoun

of P-N(imide)

in the

to give reaction

a simple of

75

(202,

X = Cl)

crystal

with

X-ray

additional

study

[3391

bipyramidal

163.5,

at

the

the

in

leads

while

points is

bridge

A recent

out via

review

deals

(NPCl,),,,,, non-geminal

series

followed

basically

supplemented

and

has

of

solution

product

probably

kcal.molV1.[340] the

of

the

bonding

in

electron

is

key

have

being been

to

three

evidence

and

confirmed

chloride.[3461

compound, possible

with for

the

transisomers

tetramer

and

both

are

was

reaction while

required,

N and

in

the

N,P,[NHC(S)NH,I,

thiourea

in in

the

S bonding.13431

gem-N,P,Cl,(NH,),,

by an X-ray

NJP,(OCH,CF,),ONa.

p-toluenesulphonyl

in

assignments

(NPCl,),-thiourea of

of

(NPCl 2 13 giving

with

with

isomers

and

N3P,C1,(NPPhs).[3441

latter of

key all

the

the

spirocyclic

reacts

N,P=,(OCH,CFS),,

for for

both

geminal

spectroscopy,

the

formation

determined

with

both

of and

2,trans-4-N4Ps(NC,H4),C1,

of mols

species.[341]

Structural

of

steps

metal

possible

n.m.r.

compound,

points only

31P

structure

Crignard

aziridine

of

all

chemistry

(ArLi,

follows

of

‘H and

substitution

N,PsC1,(NH,)(NPPh3)

sodium

that

210

centre-four

achieved.13421

from

solution

acetone

and

show

kcal.mol-‘) of

the

calculations

(H,PN),

transition

reaction

isolation

been

another

determined.

treatment

the

A re-examination

the

and

(80

group

substitution

There

three

Glycerol

126.6” 73.4”.

organometallic

main

and

by an X-ray

N,Ps(NC,H,)zC14.

(205).

both

of

that

routes

trimeric

Structures

is

view three

on the

with

study

reveals

first

distances:

Ab initio

an alternative two

trigonal

to

rings

liberates of

two

P-N(equatorial)

reduced

stabilisation

derivatives)

A comprehensive

pyridine

that

bond

and is

with

distorted

following

membered

concentrates

and

organoaluminium

structure

in

(H,PN) Z and

formation

form

actually

Compounds.

modest

a single

bonds.

phosphazenes

the

are

cyclotrimerisation

systems

P-N-P

atoms

angle

four

from

isomeric is

the

bond

the

Related

to

an

(203)

179.9-181.2

cyclophosphazenes

dimerisation paper

with

oxygen

and

model

monomer

phosphorus tion

phosphorus

but

product,

P-N(axia1)

Cyclophosphazenes

The

the

bridges

The

167.4-170.lpm;

P,N,

of

coordina-

P-O(axia1)

for

X = OSiMe,),

dimethylurea

obtained.

angle

(202,

compounds chloride

compounds

a hydrolysis such gives

as

(204)

and

structure,[3451 benzoyl

product chloride,

NSP,(OCH,CFJ),OR

and of

Ph3PC12 with

loss

of

76

Cl,

/O

~-zzdk, / N-

CH,OH

7

p-NYPNO

Cl2

CH,

N-P

'0

-\

'P' Cl'

Simple

cyclophosphazene-TCNO

quaternised

derivatives

such

salts as (206)

HN

\N-P

been

have and

isolated

(207) with

PhQ,p,O

by treating

Li(TCNQ);

'_' --u-

P-M;,,,

N//\N

I

II

I

who),P\N,F’(OPh)=

KF,CH,O),P\N/P(OCHzCF,),

(207)

(206) further

treatment

leads

to "complex"

salts

of the highly

involving from

several

N,P,(OPh),

The

remaining

halogen

observed

than

related

nitrogen

A 1:l complex

atom

in N,P=,(NPPh,)X,,

sodium

methoxide

on the basis

for n = 1-3. equal

atoms

with

formulated

N,PJ(NPPh,)(OMe),X,_,,

nearly

electrical

greater

phosphazenes.

via a ring

as

have

of magnitude

polymerised

formulated

compounds

has been

obtained

and TaF,.[3481

can be substituted products

orders

coordination

salts These

[phosphazenel'[TCNQl-.TCNO.[3471 conductivities

II

for X = F

where

to give

of detailed

n = l-5.[3491

in unequal

proportions

for X = F or Cl, a range

n.m.r.

of

spectroscopy

Geometrical

isomers

as were

for X = Cl but more

77 The

transient reacts

(NPCl,), with

copper with

aldehydes

and

(208.

R = Me,

CH,Cl

or

in

reactions

at

-60°C

R

R’

Ph.

substituted Crignards

ketones

in

the

the

/

in

to

= Me or

RZ = H or of

Ph.

LN

the

give

presence

of

novel

Seminal

R2 = H or

trimeric

Me;

Comp lex

chloride

of

formed

presence

the

Me).[3501

w ith

propan-2-01

(Bu,PCuIl,,

R = Bu’,

R’ are

either

= Me, obtained

MeLi

(209)

react

products

mixtures

, but

when

or

and

ButLi

.a small

R’ H

Yp/C
N/

cyclophosphazenes,

R

OPr’

,>P<,

OH

N’

II

I

\p/H +N

II

I

I

cl=p\flpclz N

Cl,

Cl,

N\

bN-Pk

-N\j”

yp-

Cl,

Cl*

amount

of

(210,

excess

of

propanol.13511

are

R = Me), (2091

first

and

step

in

halogen-metal The

major

N,P,Cl, the

R = Me)

are

spectroscopy, (210,

is

more

(2131.

NAptiN

-;>N_p/N

NY

P-

Me,

isolated

Six

formed

with

and

(211)

R = But).

these

alkyl

using

two

mols

and

of

with

As with

lithium

one

mol

according

products,

(2121,

(210,

MeLi, Bu*Li

is

MeLi

and

an

n.m.r.

including among

Crignard

reactions

of to

the

(209). products

reagents,

the

considered

to

be

exchange. reaction loss

of

stable

[3521

increased,

were

in

ring If

the

chlorine

the

electron to

contracted

to

mass

N,P,Cl,+.

of

(NPCl,),

N,P,Cl with

spectrometry

considered

triphosphazene

concentration

oligomerisation

impact

give

to

of have

structure e

in

%n612

the

ion

takes

source place

is

78 with

(21

NePeCl,,'

being

'NY

'Cl

(214)

(213)

New bicyclic

tetraphosphazenes is treated

N,P,Cl,(NHEt)z morpholine, expected

with

either

have

In some

product,

respects

cyclopropylamine

isolated

been

n addition

and

gives

that

a bicyclic

the

is also

NRR'),,

N,P,(NHEt),

it is surprising

also

when

piperidine,

pyrrolidine

or cyclopropylamine

substitution

isolated.[3531

(=I

with

diethylamine

normal

N,P,Cl,

species.

Cl, P-N=P-NNP-;

Cl,!

clZp\N//p\;~;CIZ_

abundant

r

N

Y

II

the most

reaction

of

product

(216).

(RR'N)

P.=N

N

-P(NRR'l,

'NEt

N

\I

II (RR'NlzP

I\

N

-N

II ‘N&H,

N

II \I Z&

LP(NHEt)

3 H 5 12

-PPNHC

(C,H,NHlP=N

P(NHC,H,l

(C,HsNH),P-N

(215)

Tri-

and

tetrafluorophosphazenes

ruthenocenyl with

mono-

phenyl

substituents and

have

dilithioferrocene

been

study

are

(217)

incorporating

two transannular

known

of this

example

1.5-N4P,F,[(CsH4),RuJ dilithioruthenocene structure

shows

conformation A series reacts

with

intriguing

type

of compound. is treated

to give

to accommodate

in addition

lithium

which

a mixture

(221).

structures

is (220). is the

first

starts

with

of mono-

and

An X-ray to a boat

substituents.

is produced

of acetaldehyde,

or

in this

N 4 P 4 F e structure

the two transannular

enolate

methyl

crystal

Production with

of the planar

of vinyloxy-tetraphosphazenes the

isolated

compound

substitutions,

or on treatment

or with

the compounds

which

distortion

further

to (221) for which

The most

determined.

ferrocenyl

or ruthenocene

Among

lithium.3354.3551

comprehensive

carrying

can be substituted

when

but only

N_,P,Cl,

79

Fe

(217)

F -_P-N=PF,

II

Fe

I

r;

N

I

F,P=N-P

I F

I

I

F

F (220)

(219)

RU

(221)

60

N,P,C1-r(OCH:CH,) The

state. [3561 spectroscopy

Following

The

are major

species

(NPC1,),,[3511

P-N-S

are complex

and alkyl

in which

Winter

lithiums

n.m.r.

unusually

the

(222) and

containing

(224) but

and van de Crampel

in the presence

heterocycles

mixtures

hydrides

among

in general

Cl,

Cl, N/p\N

in the pure

dimensional

by two

of isomers,

of alkyl

to the mixed

products

obtained

products.

with

reactions

were

was analysed

a mixture

success

extended

2-propanol

latter

to show

2.4-compounds

have

and N,P,Cl,(OCH:CH,),

of excess

(223).[357]

others

>P(OPr')H

these

thia-

H

Bu'

,>PLN

N/P\N 0

I

OJI X%N//S\X

I ,&

\ II

PhysAN//'Ph

(222) substituted than

derivatives

Z-aminoethanol spirocyclic are

react

products

replaced.[3581

0

give

smaller

Two mols

cyclophosphazenes.

(225)

in which

such

(225.

products or

to give

the two chlorines

compound

x

B/

of cyclic

1,2-diaminoethane

(223, X = F, Cl or Ph)

with

One

proportions

of either

at phosphorus

X = Cl, Y = 0) has

Phz

Cl2

N/s =N,p/Y \S -NH ‘N 41

x

0

H

(225)

been

crystallographically

atoms

occupying

formed to this

with

investigated

cis positions:

1.3-propanediamine

behaviour.

similar

showing

all three

spirocyclic

and 3-aminopropanol.

Friedel-Crafts

reactions

on

oxygen

products

are

In contrast

(222, X = Cl) with

81 PhR,

for

R = Me,

sulphur

with

both

OMe. [3591

of

separated

by

and

The

Assignments

were

ortho-para

formulation

The

salt

sodium

constant

the

of of

for

of

the

has

acid

first

transition

compound

l-

9.62

into

the

x in

“Cl,

disolvate

and

dP\

area

158.7

and

similar

it was

possible

to obtain

(m),

respectively.[3631

Related

compounds

be obtained

from

respectively

from

X = Cl)

SeOCl,

loses

II

I PhzPN

NAwcl’

N jNbC1=

(230)

product

linear

phosphazene

planar

from

ring W-N

but

with

between

(233).

acetonitrile

P-N

distances

using

the molybdenum

distances

are

either

analogue

177.3

MoCl,N

of

with

NbCl,, and

(232, M = Se or Te) can

CH,(PPh,=NSiMe,),

chloride

and or

(229)

and,

and TeCl,, [3641 and on treatment

hydrogen

a

N//p\N

(231. X = F or Cl) and

reactions

WX,.

been

Ph,

N

166.3pm:

fashion,

has

phosphaxene

resulted

Crystallisation a

Ph,Sb.[3601

lo-‘.[3611 this

II

the

containing

a

trans-

dissociation

(229)

In

n.m.r.

when

basically

(229).

I

between

conjugated

the

Phz

N

between

‘H

isomer.

with

and

as

isolated,

[H,NPPh,.N.PPh,NH,IC1.13621

(231.

isolated

metals

I

179.8pm.

and

obtained

solution

developments

(228)

falling

3’P

be

support

radical

been

ph=p%

a

can

for

calculations

determined

N//p\N

gave

chlorobenzene

cis-ortho-drtho

structure

dichloromethane

interesting

(NH,),

reaction

The

which

using

the

X-ray

persistent

in

of

I (H,Nl,PBN,30z

is

orbital

the

free

most

The

with

at

R = Me or

isomer.

forms,

assigned

an

substitution for

para

reaction

compound by

(228)

incorporation

ring5.

structurally

missing

reduced

the

on

give forms

the

isomeric

molecular

(227) is

I,

(2261.

and

Ph,P,N,SCl

or

isomeric only

possible

confirmed

isomer data

E.s.r.

One

X = Cl)

HPLC

Br

para

(223. six

.

and

Cl,

give

the

spectroscopy

Pr’,

reagents

compound

five

Et,

ortho

Other

disulphur gives

OMe,

conversion

with

to the

DBU,

82 H

HZ?

HZ PhzP

/CA

PhzP

PPh,

I

4

Cl3

Cl,

X4 (231)

Regioselectivity nucleophiles (235) give

with

in chlorine

is shown Me,SiNMe,

while A highly

(=).I3651

substitution

by formation

in (234) by

of a C-substituted

P-substitution puckered

occurs

12-membered

products

with

Cl,

Cl,

N4pLN II I

to

P-N

(OCH,CF,),

I

N4piN II I

II

Me,N-CNN,C-NMe,

‘l-‘-%

CF,CHzOLi

ring with

c1-cA N/c-c1

N"-"

(236)

(235)

(234)

rp=fJ C-Cl

Cl;C

B

N

N

Clil\P ,+ \ N=C-N :1

(237) and

C-N bond

trimeric PCl,

lengths

product

of

160 and

131pm

respect ively

(Cl,PN,CCl 1, (237) obtained

and Me,SiN:C:NSiMe,

in toluene

is

found

in a reaction

solution. [3661

in

the

between

83 5.2.6

Bonds

to

Lower

Oxidation

carried

out

[3671

Oxygen States.

using

The Group

6 elements, where

(Me,SiO),PH(X), products

A series

are

esters,

Mixtures

of

proved

ClC(OlOR

be

phosphorus(III1 are

P(OEt1,

-+

.

good

in

equations

[(EtO)PF,I-

+

(EtzNl,P(OIF

between

either

chlorine

halides

(239)

either

or

halides,

cyclic

substituted

the

chlorination chloride

examples

of

the

bromine

. . . (421

. . . (441 . . . (451

salts

OPh or

initially reaction or‘.

OEt. give

with

following

elimination X

gives

material

elimination

of

I R'R=P-0

the spirocyclic

yields is

which

observed

on phosphorus(V)

chloride.[3701

OMe 0

1

1‘ PC1

+ X-

(238)

and

methyl

behaviour (2401

of methyl

OMe

and

= OCH,HC,O)

halogenophosphonium

diarylchlorophosphite

in dichloromethane

phosphonites RI/R,

starting

Similar

phosphoranes.[3691

(241) with

for

transformations

+ (Et,Nlz(EtOlPFz

= RZ = Ph.

further

phosphonium

with

some

tetrachloride

reagents

2-methoxyphenylphosphinites.

R’

but

carbon

+ [(Et,NlsPFl+

(Et,N),PF,

(238,

with

give HP(Ol(OSiMe,l,.

. . . (431

P(OEtl(NEt,l,

Reactions

hand and

the

R,P(O)(OSiMe,l.

+ (EtO)zP(OlF

[ (EtOlPF,l-

phosphites

with

halides

(42)-(45).[36Bl

-+

+

other

to

alkyl

fluorination

and

been

oxidised

with

together

fluorides

P(OEt),(NEt,)

P(NEt,l,

are

while

on the

oxidative

reactants

summarised

has

(Me,SiOl,PH.

(ROCO),P(Ol(OSiMe,l

organoammonium

to

reactions

example, Te.

sometimes

(ROlC(OlP(O)H(OSiMe,l, have

for

X = 0 to

RP(OSiMe,l,,

Chloroformic

of

bis(trimethylsilyl1hypophosphite

2

-I

(239)

(240)

84 +H3But,

Cl

oyP’o I

I

Bu~,H,C,O-P,~

,P-OC,H,Bu',

(241)

A new the

cyclic

trioxatriphosphorinane

hydrolysis

equivalents compounds

also

been

derivative

Methylenebis(phosphinic

acid).

the useful

diphosphite

hydrolysis

of CH,(PC1,),.[3721

bridging (298pm)

than

Prolonged leads

complex,

P-bonded

ligands:

to steric

K,[Pt,(pcp14J.2H,0, the Pt-Pt

analogue

to the dimeric,

conformation of the

hindrance. of

an analogue

the

slow ligand

containing

separation

of the

stability

following

diphosphite,

of Mo(CO)JIP(OMel,l,

unexpectedly

boat

The

CH,[PH(O)(OHlI,,

Like

in the diphosphite

reaction

structure

in a distorted

can be prepared

ligand.

as

of two

4-substituted

environments.

is attributed

obtained

in the presence

and a crystal

the ring

phosphorus

to air and water

a diplatinum(I1)

has been

Related

obtained

shows

non-equivalent

compounds

(242)

of 2.6-Bu"&,H,OPCl,

of triethylamine.[3711 have

4-methyl with

product

here

forms

four

is longer

(292.8pm).[3731 with

trifluoroacetic

acid

Mo,[u-P(Ol(OMel,l,(CO~~-

IP(OMe),lz(CF,C00),.[3741 The

complex

mixture

(EtOl,P.O.P(OEt), (244) I, can

while give

(Et0

resulting

from

reaction

and Mn,(COl 1o contains

the corresponding products

such as

system (ml-(m)

with

between

compounds MnX(COls, depending

(2431 and for X = Br or on the

P(OEt1,

I (OC 1,Mn

Mn(CO1,

(OCl,Mn

I (EtOl,P\O

Mn(C013

I ,P(OEtl,

85

(EtO) 2. P '

"P(OEt)

I

(EtO) 2 P I"P(OEt)

2

I

X(OC),Mn

I

Mn(CO),X

X(OC),Mn

Mn(CO),X

I (245)

2

I I

(EtO),P\O

,P(OEt),

(246)

)2

(EtO) 2 P"'P(OEt

I 12

cocr,nn/x\?olCO

1’4

(247)

experimental for

(248,

conditions.[3751

Hypervalent

mono-

and dications,

0 or S, R = H. Me or Et),

been

obtained

and

spectroscopy.[3761 three

An X-ray

structure

is available

X = Br).

five-membered

based

investigated Their rings

(249, X = 0 or S) and

on the phosphetrane

by detailed

stability chelating

(250,

structure

X = have

n.m.r.

is related

to the presence

the phosphorus

atom

of

and by the

86 strong

basicity

A full double The

of the apical

crystal

salt,

structure

Detailed

State.

esters,

cyclopropane

for the hydrated

(251)

calculations

HPO(OMelz

n.m.r.

reported

for

on the phosphorylated

inter alia.

group

are

and H,PO(OMel.[3781

spectroscopy

has shown,

for one phosphoryl

the other

determined

Ab initio

PO(OMeln,

multinuclear

rotation

has been

MnNa(H,PO,),.H,O.[3771

+5 Oxidation

the methyl

chalcogen.

that

there

but a barrier

is free

of 75 kJmol_'

for

two.[3791

HO(O)P-

C[P(O)(OEtl,l,

0 -CH,

I

/

CFz

FzC P(O)(OEt),

\

0 -

C' \

I CF,

CH,-

Et (252)

(251)

The

synthesis

[3801 and

is reported

phosphoric

phosphorus(III1 iodides

R,PI

precursors

and

is conversion

RPI,,

followed

R,P(O)Cl

and

the

acids,

free

the anhydride. R,P(O)OH

monobasic

phosphates,

(CF,),MeC

and

in which helical the

ligands

were

PhzAs(OICHzCHzAs(OIPh,O X-ray

the

Cl,PO,

addition

groups

but here compounds

with

and Ph,Sn(NO,), show

the

where

(=).[3821 MezPO,SnMe,

are arranged groups

the chain

in a

alternate

between

the bidentate

or Ph,SnNO, pentagonal

in

is almost

trans-Ph,P(O)CH:CHP(O)Phz(L')

structures

the

(CF,)MeCH,

to form

and Me,Sn

to

acid

and

13811 together

oxide

in

of

leads

(CF,)MeCH,

for R = (CF,lzCH. prepared

step

chloride

a mixture

Two new dibasic and

and MeJSnNEt z react

structure

of new

silver

Hydrolysis

dioxaphosphepane

Ph,P(0)CHzP(O)Ph,(L),

sythesised.[3841

also

with

the first

(HO),P(0)OCHz(CFz),CH,OPo(OH),

Similar

C1,PO,SnMeJ

A number

giving

Me,PO 2 and Me,Sn

chain.[3831

related

planar.

(RO),P(O)OH

acid

alternating

with

NzO,,

and RP(O)(OH),.

the monobasic

or C,F,.

chloride

with

for R = (CF,),CH

(CF3)MezC

Dimethylphosphinic

For example, C,F,

phosphinic,

of appropriate

R,P(OlOP(O)R,.

bis(phosphates1,

n = 2-4 and

N,O,.

R = CF,,

by oxidation

ROP(O)(OH),

tetrabasic

with

where

of phosphonic,

by oxidation

to the corresponding

the dark

phosphates,

of a series

acids,[3811

have

or been

bipyramidal

87

coordination about tin in Ph&n(NO,l,. L from two oxygens of the chelating ligand and three oxygens of two nitrate groups in the equatorial positions and phenyl groups in the apical sites. In (Ph,SnNO,l,LZ. the ligand bridges between the tin atoms which show trigonal bipyramidal coordination. The phosphorus(V) pentane-2,4-dionate

complexes (253, n = l-3)

and (2541, recently prepared, are characterised by high field s1P n.m.r. shifts indicative of six-fold coordination.[3851

This has

been confirmed for (253. n = 21 by an X-ray structure which shows acac and two fluorine atoms in a plane; for (253, n = 31 the unique CF, group is perpendicular to the plane which now contains two CF, groups and the oxygens of the ligand. Me 077;

-3

F,-,(CFal,P <,

__ eYCH -C

'?" ,O--C.$ Me(CF,l,P,oGc_YCH Me

Me (2531

(2541

Although the trioxaphosphocanes

(255% X = 01 can spontaneously

dimerise to 16-membered crown type products, which can be isolated as sulphides (2561. specific synthetic routes to (2561 have now

(255,

x = 0 or NMel

(256. X = 0 or NMe) been devised.13861

An example is the reaction of (255, X = 01

with O(CHzCHzOHlz giving MePIO(CHzlzO(CH,lzOHlz oxidised by sulphur.

which can be

Subsequent treatment of the diol with MePClz

and sulphur leads to cyclisation.

A 24-membered homologue of

88 (2561

which

is (2571,

molecule

of

(255,

is produced

when

X = 01 followed

the diol

by treatment

above with

reacts

MePCl,

with

a

and

sulphur.

s

Me *p/

o"0 0

a

c 0 \ / Me

(257)

Stable

(258, X = H, n = 2 or 31 can be obtained

hydrophosphoranes

by treating

cyclic

an ammonium

or substituted

Irradiation

of

(258,

gives

where

ClP-O(CH,),-6

(n = 2 or 31 with

perfluoropinacolate.[387,3881

(258. X = SMe,

X = H, n = 3) hexafluoroacetone a pentaoxaphosphorane

Hexafluoroacetone

will

of

n = 21,[3871

inserts

while

(260).

1,3,4-dioxaphospholane hexafiuoroacetone

and

into the P-H bond

also

react

with

diphosphines

to

R'RZPPR'RZ,

tetraethyldiphosphine (a).[3891

give

With

an addition

in addition

mercury(II1

compound

dioxagives

thiocyanate

(2621 which

(CFs),CHO-P '0 I 0

(258)

with

(a).[3881

R' = R2 = Me or Et and R' = Me, R' = Bu' to produce

phospholanes

and

ammonium

(258. X = H, n = 2) in the presence

dimethyldisulphide

give

chlorophosphites

(259)

with

a

89

(CF,), (CF,),

OCH(CF,),

OCH~CF,),

(2601

(261)

C(CF,l,

0 -

I

I

Ph,P -

N

1

\

(CFsl,

(262)

(263)

(CF,),

(CF,),

/Y

/CL (CF,),

(CF,),

o/c\c=N/c\

(CF,),

ph\“\ ,P_,:” O

\C_O/C(cF3~z

/

c-o

(CF,),

(CF,), (264) Ph,PCl

eliminates

coordinate place

(2651

of

phosphorus

the

chloride

(2631.13901

thiocyanate

unit

hexafluoroacetone. (265).

mercury(I1)

bicyclic

occurs

gives in

X-ray

(2651

yielding

Use of (264).

and the

obtained

structures

are

the

five

mercury(I1)

cyanide

in

same bicyclic

when PhP(CN), available

for

reacts (ml-

with

90

Two

new phosphorus(V)

Et)

have

and

the diol

barrier

been

pentaoxyphosphoranes

synthesised (267)

from,

in ethanol;

to pseudorotation

To, s

(266. R = CHzCF,

initially,

phosphorus(II1)

data

n.m.r.

show

TX.

compound.[3921

acyclic

of the pentaoxyphosphorane

'o'(CF,),

(2681

(2681

(HO),P(O).OC(CF,),.C(CF,),OH

gives

a mixture

of

and cyclic

1

,

(cF3),

tEtO),F_,ol

s

J&O’ &OH Hydrolysis

chloride

a significant

in the trifluoroethanol

P(ORl,

or

HO(OlP-0-C(CF,l,.C(CF,),.O.[3921 The

tripod

in liquid

ligand

sulphur

Co or Ni, which metal

PIP(0)(ORl,IJ

dioxide

are

in six fold

(EL) forms

solution

formulated

with

as

coordination

stable

M(AsF,l,,

[ML,IIAsF,lz

2:l complexes

where

and

to the phosphoryl

M = Mn, Fe,

involve

oxygens

the

of the

ligands.t3931 Oxidation solution water one

of hypophosphate

gives

diphosphate

and 31P n.m.r.

la0 atom

spectroscopy

is incorporated

The mechanism

probably

'eO-hypobromous

acid

separation P-P

to give

with

evidence

metaphosphate,

attack

the

reasons

in lanthanide

comes

anion

element

the formation from

1 '601701aOPS19~

only

position.[394]

hypophosphate,

Possible

supporting

ArPOP,,

that

oxygen

on

intermediate

the Nd, Er and Yb analogues

change

to show

by a hypophosphate

flash

have

EuHP,0,.4H,O

and shows

a P-P

for the variation

in

are discussed,

pyrolysis

Enantiomers been

is

of monomeric

vacuum

2-aryloxy-1,3,2-dioxaphospholanes.[3961 phosphate

in aqueous Ia0 labelled

it is possible

Europium

of 218.4pm.[3951

distances

Further

with

by bromine but using

into a non-bridging

involves

(HO),P(O-l-P(O-)(:OlOBr. isostructural

[OJP.P0,14[0,P.0.P0,14-

prepared

of

of the thio-

by treating

91 [I-'eOl-dihydroxy-l,2-diphenylethane followed

by hydrolysis

distinguished Two

papers

consider The

phosphates

shows

ion, chain

length,

inequivalence

Crystals contain

hydrogen

spectra, shift

bonded

bond.[4001

phosphates

have

tetrahedra

form,

there

by X-ray

state

the second

each

which

oxygen

are

shows, the

acid

by water

forms

one

of hydrogen

increased

in the O-H...0

investigation

linked

of which

for a series

showing

has been

and

between

from an X-ray

crystallography

counter

[3991

of

distortion

hydrogen

bond

the

strength.

phosphates,

(cyclohexylNH,l,HPO,[4O3],

MgNH,PO,. 6H,O,

struvite,

coordination,

strength.

dimers,

for two further and

=lP n.m.r.

is a correlation

data

increase

Me4N[H,P041.Hz0[4021 determined

H,PO, ether,

analysed

with

can be

of condensed

hydration

cell while

and P-O bond

X-ray

been

Structures

14011

of m.a.s.

due to phosphorus

the unit

to the crown

hydrogen

aspects

of H,P04.3H,0.K(18-crown-61

molecules

PO,

=-Si

chemical

The two forms

[3981 for a series

crystalline

within

as with

isotropic

changes

chloride,

spectroscopy.

different first

thiophosphoryl

170-water.[3971

by 31P n.m.r.

spectroscopy.

that

with

with

and hydrogen probed

have

been

bonding

in

by neutron

diffraction.[4041 Aluminium has been unknown have

orthophosphate

been

optimised;[4061 AlO,F,

heteropolyanionic has been

new mixed

of the

A high has been important presence and MnO,, three

sheet

structure. and from

interaction

three

form

identified feature of three which

dimensions.[4121

The

have

been

n.m.r.

diphosphate

of mixed

prepared

at 2.5 CPa and 6OO"C,

diffraction.14111 of

manganese

interlinked

phosphate,

are

[4101

powder

in the structure different

are

with

a

groups.[4081

A vanadium

to the formation

of Mn,(PO,l,,

by X-ray

atoms

phosphate

and Na,Bi,(PO,le,

of vanadate

PO, and

to give

of LisIn,(PO,l,

the thallium

different

systems

tetrahedral

vertices

system.[4091

in all cases

state

The structure

of di- and triphosphates. pressure

contains

system

the previously

or solid

by common

Na,Bi(PO,l,

phosphates,

points

aqueous

in Tl,PO,

in the Na,POa-BiPO,

and arsenate analogues

connected

to oxygens

identified

in the Al,O,-P=O,-Hz0 for obtaining

the compound

units

determined,[4071

coordinated

study

from either

Na,AlF,(P041,

octahedral

Two

formation Conditions

reviewed.14051

Mn7[P0,(OHl14(P0,1~ polyhedra,

by PO,(OHl

structure

of

MnO,,

An is the MnO,(OHl,

and PO, tetrahedra

in

(H,O)Fe,(HPO,),(H,PO4),.-

92

4H,O,

obtained

by long

reaction

phosphoric

acid

at room

phosphate

layers

alternating

phosphate

layers

contain

and O,P(OH)

O,P(OH),

A triply

water

group

isolated

with

group

sharing

is found

from

and 85%

iron(III1 The

vertices

with

both

phosphoric

has also

been

in

the reaction

acid

of trifluoromethanesulphonic

a V,- 0,SO

of

layers.[4131

Fe0 b octahedra

O,P(OH)

H,Os,(CO),(~',-0,POH).

presence

with

iron powder

consists

tetrahedra.

bridging

H,Os,(CO),(!J,-CH)

between

temperature,

saturated acid;

synthesised

of with

P,O,,

the analogue

and

in the

containing

its structure

determined.[4141 Treatment

of

[Co(NH,),(PO,)I

tCr(H,O),(H,PO,)]"+ [Cr(H,O),-12+ Water

and H,PO,-

molecules

thiolate

have

ligands

obtained

for the

are

found

1.r. spectra their

have

H'-Caa'

hydrogen

decreasing

been

detected

with

crystallisation

to the water

spacing

Half

compound

and and

two structurally cell,

which

phosphate

from

leads

different

to TiH,.,,Ca,.,,water

1310 to 1020pm

copper

H+-Cu2'

form

of crystallisation.[419]

phases,

1 and zero molecules

in similar

by PO,(OHl

temperature

the temperature,

exchanged

2.5,

at room

in the unit

on Y-titanium

the basal

Na,o[Pt,(p-PO,),linked

the anhydrous

as showing

groups

has also

deprotonated

Zn(HP04).H,0.t4181 H,O.

but on raising

material.[4201

complex,

thioether

for the

structure

doubly

ZnO, units

interpreted

bonds

exchange

(PO,),.,. 5H,O.

The

recorded

HPOaZ-

ion from

complex

amine,

is available

derivatives

been

non-equivalent length

in solid

of a-Ti(HPO,),.

deuterated

-180°C

ZnO, and

platinum(I1)

by halide,

prepared

tetraphosphate Both

(C,H,N,0,1.[4171

bridged

complex.[4161 recently

of this

investigated.14151

and a structure

guanidine-diplatinum

tetrahedra

been

gives

of formation

can be replaed

bis(tetrahydrothiophene1 been

[Cr(H,O)hlz+

in the quadruply

[Pt,(~l-HPO,),(H,O),l"and

with

and the kinetics

in the anhydrous

TiHCu,.,(PO,l,

of water

exchanges

is lost

have

of

on the same

material.[4211 Histidine proceed

intercalation

via partial

Zr(HPO,l,(Hist)

into Y-zirconium

replacement

0.,.1.9H,0

followed

Zr(HPO,),(Hist)o.,.

0.8H,O

interlayer

is 2290pm

spacing

as a bilayer.[4221

With

of the

phosphate

interlayer

by successive

lysine

molecules

and arginine

are

to

to give

conversion

and Zr(HPO,),(Histlo.,.3H,O, and great

appears

water

to

where

the

intercalated

on the other

hand

low

93

uptake

leads

at higher

to one or two monolayered

loadings.

Y-Zr(HPO,l,.ZH,O which

undergoes

31P n.m.r.

M.a.s.

show

two phosphate

exchange

phases

with

but

there

measurements

environments,

phosphate

is disorder

on

only

one of

and phosphonate

esters.[4231 Diffusion

of

intercalate

[Cu(phenl,12+

of o-zirconium

ZrH l.,[Cu(phenlzlo.,O can be

stage

units

and

groups.

each

170".

Three

three

with

K,P,O,.[4261 alkali The

metal

double

and P,O,

here

octahedral

The

with mirror

two fold

units

a

two symmetry

of four

mixed

have been

and

symmetry.[4291

the triphosphate

by Na-0

group

interactions

An

hydrogen atom

and

bonds of a

triphosphate.

from aqueous

solutions

chloride.[4311 collected

for the

of High

resoluti

I and

II

and for Na,P,0,0.6Hz0.[4321 have

been

BaNaP90,.3H,0,[4331

6H,O,[4351

HgK(Ps091.[4371

when

contains

at an oxygen

and manganese(II1

structures

trimetaphosphates:

isolated

data

by an

of MnNa,P,0,,.12Hz0.[4301

A crystalline

of Na,P,O,o

obtained

in which

together

to 300.3pml

has been

s1P n.m.r.

crystal

units,

have and

is 132.7".[4281

units

is the formation

273.6

triphosphate

Na,NiEPS0912.

nitrate

InO, octahedral

to 500°C

ion with

in the structure

5Hz0

angle

i.e. P,O,

P,0,,6-

are ca.

M = Na, K, Rb or Cs.14271

contains

was heated

are held

phosphorus.

state

diphosphate

angles

of iron(II1

CaNb,O(P,O,,l(P,O,l,

ions,

a

diphosphates.

where

the P-O-P

well

octahedral

and Fe,(P,0712(0Hl.12H,0,

LiInP,O,,

mixture

point

modifications Full

with

in which

co... 0 separations

solid

The P-O-P

iron

solutions

[MnP,0,,.3HzO13-

bonds

ammonium

conformation

MNO,

phosphate

NH4MnZPJ010.

sharing

on heating

product,

interesting

a pure

by heating

face

to itself

1358pm.[4241

in FeHP 2 0 7 can be replaced

is o,B,Y-coordinated,

terminal

soluble

of

obtained

contains

KFeP,0,.4H20

the tetrapolyphosphate

hydrogen

uptake

and the protons

CaCO,-Nb,07-H,POs

Discrete

V,(P,O,lJ

of staggered

from aqueous

groups

different

at maximum

l,lO-phenanthroline

separation

C, symmetry.14251

diphosphate.

An unusual

interlayer

types

sparingly

prepared

while

and H,PO,

H,PO,

K,Fe(OHlP,0,.2.5Hz0, been

with

diphosphate,

of V,O,,

of the diethanol

leads

to give a-Zr(HP0,1,(phenlo.,.2Hz0,

1 phase

Vanadium(III1 mixture V,O,

(P041,.3H,0,

intercalated

ordered

into layers phosphate

determined

(NH,),Na,Hg(P,O,),,[4361 cobalt

[Co(P,0,1z(H,0141'-

ammine anion

for the following

Co(NH,l,(P~0~1~.4H~O,[434l

derivative with

trans

and contains arranged

the Pa09

94

units. The

tetrapolyphosphate,

isolated 155.7

ion with

[P,O,,lh-

and

165.2pm

chain.[4381

with

Structures

linked

first

PbCO,

varying

between

along

the

in the anion

investigated

are

recently

two crystallographically symmetry),[4401

Cs,P401,.4Hz0

(containing

centrosymmetric

anions

by SrO,(H,O),

polyhedra

isolated

and H,PO,

compound

atoms

the

two-fold

Pb,Cs,(P,O,,)(PO,l,, cs,co,.

distance

of distances

tetrametaphosphate

(containing

with

).6H,O

and Sr,(P,O,, origin.

contains

independent.t4391

Li4P40,,.5H,0 rings

bridge

alternation all phosphorus

of the cyclic

independent

P-O-P

some

In PbJP,O1,,

crystallographically

include

ICo(NH,),lzP,0,,.5H,0,

and hydrogen

from a solid

state

at 400°C.

is interesting

containing

both

P40,,

lithium

phosphate

cyclic

at the

bonds).[4421

reaction

between

as this

and

[4411

is the

infinite

chain

anions.14431 In a study

of

Li,P,O,e

led to pure

The

unit

repeat

the first

five, period

crystal

tetrahedra together

that

NbO,

shows

octahedra

barium

dimensional

(269) and -* structure.[4491

large

CrO,

with

in BaCs,(P0,),.[4471

layers

of linked

Dark

transport

green

chains

contain

PO, tetrahedra

through

of

crystals

in chlorine,

with

PO,

of the NbPO,

framework

extending

at the

the

0

I

/O\

the

in palmierite-type

octahedra

channels

is

while

in which

0

O\

in Pb,Li(PO,l,

and a refinement

by chemical

sharing

ends

LiH,PO,

show a structure

and PO, tetrahedra.[4481

of edge

seeding

observed,[4451

[4461 and four

about

a three

chain

has been

for BaNb,P,O,,

octahedra

of (x-CrPO,. obtained chains

this

is eight

data

are grouped with

structure NbO,

in the polyphosphate

time

in LiCs(PO,),

Single

dehydration,

hexaphosphate.[4441

,O\’

A0

/O\

o/p~oICr\o/Cr\O~P I 0

A0

0

(269)

The

new molybdenum

mixture

of Cs,MoO,.

tetrahedral

Mos

phosphates, MOO,.

cluster

Cs,Mo,P,O,,,

MO and P,O,

each

obtained

at 900°C.

face of which

from

contains

is capped

a 3:9:3:6 a

by a p3-

95

oxygen.[4501 atoms

The

forming

P,O,

ligand

Two open

have

H,PO,,

former of

of

the

three

is

original

iron

mixture.

been

aluminophosphates, tetrahedra

The giving

template.

Both the

is

in

cluster

of

AlO

are

best

and

two

PO,

of

and

three

is

one

the

latter in

the

new hydrated on a framework and

of

A104(HzO)z

Al,,P,,0,,.4(piperifrom

i-propylamine

octahedral

octahedral

The

available. of

isolated

using

representation from

by two

consisting

and

and

a mixture

impurity

based

was

Fe,P40,0H,o heating

tetrahedra

compound

AlPO,-14

tetrahedral

built

(270)

second

mainly

groups.

hurealite,

a number

AlPO,.l.SH,O, between

a chelating by P,O,

sodium

details for

molybdenum

acetone.[451]

mineral

7A1P04.2Pr’NH,.2Hz0,[4531

preparation

shown

by

and

mount

structural

interposed

dine.Hz0).[4541

and

the

determined

including:

octahedra.[4521

structure

of

a small

carry

bridged

phosphates,

Fe(C0j5

analogue Full

have

are

hydrothermally

Bu).

from

each

edges metal

prepared

arising

equivalent

tetrahedron

slant

transition

been

a pure

Structures

present

the

R,NOH (R = Pr or

alluaudite

PO,

crystallographically

base

framework

NaFe,P,OIz. of

the while

three

a as

aluminium

the

units

are

A17P,0,e(OH),.2Pr’NH,. aluminium

A10 4 unit

to

eight-membered

units give

rings.

The connected

a five

atom

Two of

these

as

Y

O, A0

/A1\ I

0

O\ P / 0'

\

OH

0

O,J /O

0

\ Al

ei, \0

/O

'0 1 OH

o/A1\O \ 0

units

are

chains as

The

linked

formed

[Pr’NHs]+OHfinal

into

by

cages

further connecting

compound

is

by

cross two

a precursor

two

PO,

aluminium of

tetrahedra The

linking.

atoms

AlPO,-17,

and

amine in the

is

the

zig-zag encapsulated framework.

analogue

of

the

96

zeolite acid

erionite,

and

is obtained

and piperidine.

consists

with

framework

oxygen.

Figure

The AlPO,-17

a tetrahedral

phosphorus

2.

remove

network

bridging

In these

the templating can block

hydrogen

chloride

recently

been

compound

for

in Figure

2,

atoms

by an extra

it is not always

easy

to

by permission

from

1986)283).

by c alcination

sites.

at 420K

shown

(reproduced

C42

alum ina, phosphor ic

alumin ium and

two aluminium

structure

active

found

structure,

systems

Crystallogr.,

material

hydrated

of alternating

between

The AlPO,-17 Acta

from

Treating

16 hours

to be effective

and carbonaceous with

methanolic

in a sealed

and causes

system

has

no adverse

effects.[4551 Structures

have

aluminophosphates prisms

using

structure

the

sheets

five-membered

determined

discussed

i-propylamine

with

corrugated

been

framework

rings

consists

of crosslinking

to give

aqueous when

is similar

sharing

between

units

of five-

enclosing

the protonated

(NH,l,(PO,Fl.H,O

solutions

the products

of the mixed

of either

route

and

are disordered

a framework

of

between

three

over

two

Gas(P0,),0H.PrsNH,.1.09Hz0,

by gallium

samples

as

in five-fold

molecules

polyhedra

by a new synthetic

of the

obtained

to the AlPO,-21

by crosslinking

gallium

structure,

analogues

for GaP04-21,

gallium

Crystalline obtained

of edge

The template

The GaPO,-14

coordinated

formed

containing

sites.

That

as template,

of ribbons

coordination.[4561

for two gallium

above.

based

(NH,)HF,

can be precipitated

fluoride-fluorophosphate,

and

six-fold

and phosphorus

and K,PO,F on reaction

or KHF,

tetrahedra

amine.[4571

with

can be of concentrated

phosphoric

by ethano1.[4581 K,F(PO,F).

which

acid

Crystals are

97

isostructural the

with

components,

Co(PO,F).3H,O, contains

K,F(SO,l

obtained

tetrahedral

by hydrogen isolated

PO,F

decomposition

for mixed

been

obtained

solutions

of KPO,F

and X-ray

studies.[4611

phosphate-vanadate

in unit

cell

with

units

held

and copper(II1 X-ray

fluoroapatites,

dimensions

chloride, together

Cu,K(PO,F)(OHl.H,O

for M = Ca. Sr or Ba and x = 1-3. have inrease

COO,

insoluble

together

of

and cobalt(II1

and octahedral and

by melting

The structure

from Ag=PO,F

bonding,[5601

from aqueous

thermal

have

KF and K,POsF.[4591

has been salts

powder

for data

M,,(PO,l,_,(VO,),F,

been

analysed

increase

to show

an

in vanadium

content.14621 POF,

is eliminated

heated

giving

possible

to convert

Manganese potassium

salt

and,

were

High

via

obtained

presence

of the

and

reactions

of a range

of metal

M(Il,M(III)P,O,N.

where

M(I)

or Mn.[466,4671

A magnesium

result

from

the

zinc acetate.14641

The process

and

anion

starts

with

(PhOl,P(O)NH,.

coordinate

between oxides

it is

imidodiphosphate

reported.[4651 (PhO),P(OlCl,

and a normal

temperature

are

similarly

M(HPO,NH,l,,

MnC12

salts

M(PO,F,l,.

in 50% yield.[4631

(PhOl,P(OlNHP(Ol(OHl,.

(PhOl~P(O)N:PCl,. data

to H,PO,F

respectively,

has been

proceeds

M,(PO,F);

amidophosphates,

for preparing

[0,P.NH.P0,14and

difluorophosphates,

HPO=F,

and zinc

a new method

POCl,

when

monofluorophosphates,

Detailed

i.r. and Raman

analysis

carried

(PNO), gives

and Na,PsO1,

nitridophosphates,

= Na or K and M(III1 analogue.

out.

in the

= Al, Ca, Cr, Fe

Na,Mg,P,O,N,

has also

been

prepared.

5.2.7

Bonds

to Sulphur,

Phosphorus(IIIl-Sulphur been

trapped

(~1,[4681

with and

Selenium

Compounds.

o-quinones

further

data

or Tellurium Thermally

produced

as the cycloaddition are available

PhP:S

has

products

on the stabilisation

of

98

of such

two coordinate

4-MeOC,H,,

in molybdenum

etc.,

Among

complexes.[4691 dehalogenation been

compounds

from ROP:S

such

Structure investigated

tend

(272,

prefers

and

a preference

As,Se,

system

by thermal

are

amorphous

(RO),P(O)NH,

while

give

RNH,

with

), has been

of phosphorus, and arsenic

basal

atoms

phosphorus

shows

occupancies

spectrometry.

temperature gives

and X-ray

in the series The

ranges

and

in the

A,B,

HCl,

species

of

and an

etc.,

was

(274)

have

ruled

and

sodium

with

to give

No reaction

occurs

azide,

The properties

including

with

P(SEt),

and

been

from

to (a),

reviewed.14751

PS,-,

stabilised

the reaction

solution.[4761 out by thermal

of trift-butyl)-

its conversion

desulphurisation

anion,

is produced

in acetonitrile data

tetrachloride

react

(EtO),P(0).N:P(SEtIz.

Compounds.

(275).

trithiometaphosphate salt

for R = Et or Pr.

(EtO),P(O)H

the monophosphazene,

the phosphaindane

X-ray

filling

of the P,S,-P,Se,-As,S,-

decomposition

of carbon

phenyldithiophosphorane

arsonium

mass

positions

in an

(273

of all compounds

and RNH,C1.[4741

Phosphorus(V)-Sulphur

H,S

melt

with

by annealing

amines.

in the presence EtSNHR

to MeOH,

As&S,

n = O-4 and m = 0-3.[4731

region

aliphatic

(EtS),PCCl,,

Ccl,

density

positions,

Analysis

methods,

been

phase.

Primary P(SEt),

position,

have

at those

phosphorus

and basal

formation

influenced

P,Se,-As4Se,-As4S,

from

system."[4711

of a 2:2:3

Although

phosphorus.

where

unknown

stabilisation.

and electron

electron

P-dimorphite,

apical

and P&S,

charge

heteroatoms

homoatomic

sublimation

indicates

P,As,-,S,Se,.,. existence

with

for the apical

35 and 35%

P,S,

connectivity

or deplete

between

of 43.

has also

for the previously

P,S,,

to locate where

sulphur.[4721

disordered

diffraction

for P,S,.

isostructural.

by vacuum

arsenic

the

by retro-cycloadditions

the rule of topological

isomorphous

was

Evidence

X = OR or NR,).[4701

to accumulate

P,Al,S,.

are

generated

structure

isoelectronic,

obtained

experiments

R = Me, Et, Ph,

carbonyl

Na[CpMo(CO),l.

trapping

reactivity

"nature

i.e. that

with

where

investigated

and R,NP:S

using

in a molecular level

as

and

RP:S

and manganese

the reactions

of RPSCl,

produced

derivatives

thioxophosphines,

at

110°C

to

reactivity

The monomeric as a tetraphenylbetween

Successful motion

and

P&3,,,

refinement

problems

KCN and of the

but a pyramidal

99

(274)

(275) C,H,Bu+, oI

7

,P-CsHzB&

Bu',H,C,-b\S

(276) structure predict

is

suggested.

a planar

rigid,

a solid

initial

SCF-MO

structure state

reaction

also

in

pyramidal yields

the

calculations

gas

phase,

structure the

known

zinc

and

on the but

cannot

if be

the

other

hand

molecule

ruled

out.

is The

cyanodiphosphate,

(NCPS,.S.PS,CN)=-. Coordination via

the

copy.

Me,PH:S

atom

to

according

to

cadmium

recent

halides

i.r.

and

takes

place

Raman spectros-

14771

P,S,o with

continues

sodium

phosphate hedral the

of

sulphur

two

azide anion,

geometry aside

to

be

in

acetonitrile

a versatile

[PSz(N,)zI-.[4781 with

nitrogens.

a small

reagent, salts

of

The (93.8”)

angle

giving the

anion at

on treatment

diazidodithiohas

distorted

phosphorus

tetra-

between

The related reactions of P,S,, with

NC”-‘, /sLp/-s_CN -S-P=6

n

100

sodium

cyanide,

bridged

anion

distances

on the other (277).

of 212.1

the bridging Benzonitrile

results

P,S,,

when

and P,S,o

are

the

159.6

and

and

initial

second attack

rich

fluorides

with

P-S

and a 122.6"

angle

the diazide show

162.0pm

order

at

in either

(278) based

in comparison

salt,

on the

by P-N-P.

with

P-S-P

P-N angles

to 130.0".

disulphide

in methanol,

at 0" to 35°C which

gives

is first

is controlled

order

kinetically

by

on P,S,o.[4811

sulphides,

acetonitrile

of

above.[4801

is replaced

the reaction,

of the alcohol

phosphorus

link

and

in carbon

mentioned

the anion

is opened

product;

salt

as the tetrapropylammonium

one P-S-P

angle

of P,S,,

as the sole

Sulphur

of the sulphur

the diphenyldithiazolium

anion,

compounds

in which

Methanolysis

in P,S,"

reacts

the P-N-P

106",

(MeO),PS,H

salts

and terminal

respectively

give

the same

for both

distances

184.5pm

and P,S,,

structure

of ca.

and

gives

hand.

has bridging

sulphur.

(P,NS,)V,[4791

Structures

which

P,S,,,+,, react

with

metal

or 1.2-dimethyoxyethane

sulphanebis(fluorodithiophosphate)

mixtures

to produce

(S,PF.S,.FPS,)"-

for n

= l-8.[4821 Treatment selenides. which

of

for M = P, As or Sb,

coordination

Silylesters. synthesised

in high

esters or But,

with

yields

ring

where

from

to

RP(SiMe,),

and elemental

stannyl

esters

readily

obtained

Low temperature

trithiophosphonic

S,Cl,,

closure

(279)

solids

n = 3-5.

to give

acids,

at -3O"C, both

(279).

or in

atom.[4831

related

as white

5 sulphides

[CpFe(CO),(R3MX)I+

R = Me, But or Ph, can be

are more

Me,SnCl.

free

isolated

chlorosulphanes undergo

yield

The

but they

derivatives

the Group leads

is via the chalcogen

RP(S)(SSiMe,),

toluene.[4841 similarly

with

[CpFe(CO)z(THF)I+

R,MX

in

can be prepared by treating

silyl

hydrolysis

of the silyl

RP(S)(SH),

for R = Me

and on reaction

the silyl These

sulphur

and

stannyl

compounds

are

with esters

101

J Z-

SiMe,

SiMe, /

\

N-P

5

-S-

!lHSiMe,

c .kiMeJ

.?!iMe,

(281) stable

(282)

in

the

solid

state

but

(283)

disproportionate

and

oligomerise

in

solution.[4851 Recent

n.m.r.

results

phosphorothioates charge

and

Cyclic

the

is

singly

pyPS,Cl,

disilazane

also

phosphetidine on treatment into

(283).

The

methyl

treated

The

the

S.

e.g.

the

Ph and

group

to the

(281)

NH, CHzO or

is

give

bidentate

R’

= Me or to

tin

i.r.

the

with

diazadi(282);

dithio-phosphates compounds

in

and

order

metal

of

Et, and

have

monodentate

n.m.r.

for

on the

313.01249.5pm

about reduced are

where

n = 1-3,

R

this

has

been

PhCe[SP(S)(OMe),l,.[4891

other

hand

shows

aniso-

7

(265) with

P-S

respectively

coordination

periodic

dithiophosphate

spectroscopy;

structure

(284)

their

derivatives.

R4-,Ge[S,P(OR’),I,,

X-ray

complex

character

190.3pm.[4911

react

are

converted

(284)

is

(SICNH)

Hexamethyl

monomer

n

ligand

in

negative

a base.[4871

via

transition

derivatives

by a partial

dimethyl

distances

that

C,H,(XH)(YHI,

of

betaine

concerns

before

according

confirmed

carries

= 0.

presence

iodide

and main

are

Organo-germanium groups

X.Y

probably

section

-phosphinates,

= Me or

with

showing

[4881

following

groups

the

(281).

with

largely

reagents, in

as

phosphorus.[4861

(280,

reacts salt

interpreted

atom to

when bifunctional

betaine,

been

sulphur bonded

dithiophosphates

obtained the

have

and

and

tin.14901 even

243.6 Cyclic

and

further 341.lpm

Sn-S

very

distances

distorted

The bidentate in

of

193.2/203.1

octahedral character

Ph,Sn[SP~l

and

dithiophosphinates

P-S

and

of

the where

distances such

as

Sn-S

203.9

and

(285.

R = Me or

102 Bu')

can be produced

by oxidising

R,SnH(CH,),PHPh

with

sulphur.[4921 Structures

have

been

Bi(S,PPh,),.[4931 which

the antimony

coordination thus

similar

short

Sb-S

except

to the apical

activity

of the

atom

lone pair

are also

in these

available

from

Ph,SbOAc

with

the corresponding structure

either

(286) with

i”

i :

Ph,P

As this

stereochemical

PhzSb(SOPPhzl was

or the sodium

prepared

salt

and,

has a centrosymmetric

and two

longer

Sb----S\ I /:

Sb-S

YS\

\

is

through

systems.

Ph,P(S)SH

one short

bismuth

and 330.lpm). against

for Ph,Sb(S,PPh,),

dithioarsinate,

plane

longer

about

The dithiophosphinate

and Ph,Sb(O,PPh,)[494,4951

in

pyramidal

dimerisation

(317.3

it is evidence

molecules

The basal

and three

is effective

Bi... S contacts

intermolecular

pentagonal

Coordination

there

and

isolated

ligands.

(mean 259.5pm)

that

Sb(S,PPhz)J of

is in distorted

distances.

is trans

Structures

for both consists

anisobidentate

two short

(292.3-318.7pm) very

former

atom

by three

contains

reported

The

y”’

LCpzvh

as for

dimeric

contacts

giving

PR,I+[S,PR,I-

’

(286)

an eight-membered phosphinate

Sb,S,P,

structures with

dithiophosphinate, Antimony

chains.

coordination occupied sulphur

by treating

and

also

atoms

are

different

ligands

leading

in pseudo-trigonal

by two oxygen

phenyl atoms

groups

and

from

that

of the

to infinite bipyramidal

with

axial

or by one oxygen

positions

and one

atom.

In the vanadium

solution,

bridging

to two equatorial

either

The thiophosphinate

ring.

are completely

Cp=V

complexes with

(287. R = Et, OEt or OPr')

the appropriate

the dithiophosphorus serves

Fe[S,P(OPr'),l,

as the counter have

been

group

disulphide

obtained

[R,P(SlSI,

is coordinated

anion.14961

Stable

for the first

obtained in THF

in the cation crystals

time

of

by treating

103 either

iron

metal

or

solution.[4971 distorted

Fe,O,

The molecule octahedral

246.1.

249.2

unidentate

and (Fe-S

with

dithiophosphinate

each

and

monomeric

R/R

from

in CDCI,

centres,

while

of

molecule.

[5011

range

nitrogen

bridging

ethanol

or

a ligand

one

nitrogen

the

is

to

C,,

ligand

symmetry

to

is and

compound

two

donor, gives

ionic

dithiophosphate

[ZnL,jfS,P(OR)z12

ionic

compounds

structures show

and one

to

of

the

zinc

while

where

with

a

in

for and

two bipy

nitrogens

and

group.{5021

ligand

sulphurs complex,

sulphurs

from The

thiophosphate are

in

at

chelated

NN’-Me,en

fold

en adduct,

phosphate

Two other

L = en or

five

the

In the

coordination a

the

asymmetrically

atoms

unidentate

the

with

groups.

point

and

for

strongly

en nitrogen

fold

compound

data

zinc

ethylenediamine,

zinc

ionic

groups

bonding

distance The

zinc.

l,ll-diamino-3.6.9-triazaundecane,

hand,

an

five

between

N-tetramethyiethylenediamine,

only

donors

Et

most

l,ll-diamino-3,6,9-triaza-

anisobidentate

nitrogen

R -

dimers,

a solvent

addition

groups.15031

contains

where of

conductance

compound

irregular

irregular

Pr or

IRh(CODICllz

groups of

group.[502,5031

one

R = Et,

with

presence

X-ray

to

where

pyridine,

and

thiophosphate

three

1:l

form

including

i-propyl

coordinated

again

the

coordination

symmetrical

one

coordination

all

the

Zn[S,P(ORl,],,

to

terpyridine,

of

unidentate

giving

is

close

fourth

reactions

THF solutions,

compounds

dithiophosphate

terpyridine but

in of

symmetrically

dithiophosphate

with

donors,

with

unidentate

zinc

has

reducing

of

point

N,N’-dimethyl

adduct

zinc

from

iron

202.6pml.14981

The

from

on solutions

The

[SOZI.

coordination the

and

distances

data.[5001

2,9-dimethylphenanthroline.lS031

chelating

and

Mo,S,(SzPEt,14.

Rh(COD)[S,P(ORl,I

toluene

N,N’-diethylenediamine,

pyridine

Fe-S

in CpFe(CO),[S,P(OPr’),l

molybdenums

n.m.r.

two

in

ionisation

undecane

hexane

Ce symmetry

an almost

isolated

=‘P

or

involving

of

in

unique

ligand.[4991

= Me,CCMe,,

probably to

ligand

carrying

of

measurements

Pr’,

overall

194.4

dithiophosphates,

are

N.m.r.

a pair

acid

Cs.

Rh(I1

Pr’

or

metal

free

shows

compound,

symmetry’

The

P-S

cluster

chelating approximately

with The

232.2pm:

between

the

coordination

247.2pm.

The molybdenum

bridges

with

five

on the

other

cation

and

two

compounds

have also

been

isolated.l5031 Zinc process

dithiophosphates promoted

by

are amines

hydrolysed such

as di-

by atmospheric and triethylamine,

moisture, to

a

give

104 the tetrazinc

products,

Zn,O[S,P(OR),I,

Zn,S[S,P(OR),1,.[5041

The

with

dithiophosphate

almost

pairs

symmetrical

of zinc

Under

atoms.

Zn[S,P(OEt),1,.2,75Et,NH EXAFS

2.75.

tetrahedral

data

latter

and small

contains

anhydrous

amounts

a Zn,S

groups

tetrahedral

bridging

conditions,

structure

analogous

where

Zn,O[S,P(OBu),l, to that

salt

for the thio

core

between

the amines

and ZnIS,P(OPr'),l,.nEt,N,

for the basic

of

gave

n = 1 or

point

to a

analogue

above.[5051 structure

The Cd(S,PEt,), one chelating eight

and

membered

Cd,P,S,

found

centrosymmetric

ligand

giving

previously

dimers

a distorted

The exocyclic

ring.t5061

as had been

disordered,

contains

one bridging

ligand

for a related

with

chair

type

is

zinc

compound.[5071 There

is dodecahedral

coordination

about

La[S,P(OEt),l,[(PhCH,),SOl,

from

chelating

and oxygens

phosphorus

ligands.[5081

This

of behaviour europium

groups

by

the

formulated

lanthanum

almost

and the neodynium

lanthanoids,

compound

three

of the dibenzylsulphoxide complex type

second

from X-ray

represent is shown

diffraction

~Eu[S,P(OPr'),l,(DMSO),)(Eu[S,P(OPr'),l,~.[509l coordination

is maintained

in the cation

shows

seven

for europium fold,

in

symmetrically

ionic

as Dodecahedral

in the anion

pentagonal

one type

by the

but

the metal

bipyramidal

coordination. A compound the

Ti,P,S,,

previously

to the P,S,2-

from

P,S,=-

anion,

unknown structure

by replacement X-ray

obtained

which

(two PS, tetrahedra

of a bridging

structure

the elements

the compound

sulphur

at 400°C

contains

is structurally

related

sharing

a common

by an S, unit.[5101

is formulated

edge)

From

an

as

Ti4(PS,),(P,S,)(P,S,). Reactions Pri,

Bu',

between Hex'

metal

or Ph.

aminophosphinates, Co[5121 membered are

and

similar

M[Et,P(S)NRI,

Zn, and

chelate

rings.

to those

and Li[Et,P(S)NRI,

where

R = Me, Et,

hydrolysable n = 2 for M = Ni[5111,

n = 3 for M = Ti. V or Cr. containing Ligand

field

parameters

four

for Et,P(S)NR-

for R,PS,-.

Biuretodithiophosphate monothiophosphate

halides

lead to readily

(288) can be converted

(289) and the phosphate

successfully

(~).I5131

to the

105

l-

s\ /s

s\

HNAP\NH

HN /’ I

I

O=d

P=O

\N

’

o=C\N

for

reaction

‘N/

463K

, whose

structure

(292)

is

formed.[5151

also

is

(290)

Raman

P,Se,.[51

at

P&e,1

and

The

41 c- P&a,I,

(291)

is

resonance

major but

related

to

new that

SeAP’

I

of

I l-P\P/Se

(292)

The

P-Te

order

of

butyl

and

in

Compounds.

p-MeC,H,TePR,. R,P, be

by

R = Pr’

by

usual

separation

in and

obtained

in

this

vacuum

But,PTe

is

distillation

analogues

tellurophosphonium

mixtures

of

products

and

methods.

236.Bpm,

compound

category

from The

spectroscopic

this

dimethylamino to

compounds

Bu*,

di-p-tolylditelluride.~5161

purified

the

New or

and

can salts,

its

be

to

equivalent methyl,

converted

a

bond

i-propyl, by

methyl

iodide

method

for

(R,PTeMel+I-.[51Bl

ARSENIC

5.3.1 The

and

1.5,15171

benzene

5.3

where

can

P-I

\

I

Phosphorus-Tellurium

yellow,

a-P,Se,I,

I

(291)

characterised

the

Se

I

diphosphines

of

spectra

selenoiodide

Se

Se\p/Se

Raman

product

a

Se/9\‘P-I

are

VH c=o

o=;

l!l

Compounds.

available

I=-P4SeX

l-

p\

HN ’

NH I

(289)

Phosphorus-Selenium

are

,/

B

(288)

now

C\

/=O

A

are

l-

,.y

Polvarsines reaction

preparing

pure

in

and

Arsenides

equation

samples

of

(461

provides

polyarsines;

a on

convenient account

of

its

volatility

106

n(MeAs1,

R =

+ 5nRAsH,

-+ 5(RAs),

, . . (46)

+ SnMeAsH,

Et or Pr. n = 5

R = Ph or 4-MeC6H4.

separation

of methylarsine

otherwise

the product

intermediate

first

with

obtained

As-As

with

the

related

of

in a twist

two uz-n2-Asz

of

230.2pm),

(MeAs),

compounds,

and

the polyarsine

ring

(227.2,

necessary

polyarsine

structure

containing

of a mixture

[5211 and

is, indeed.

in 1967 shows

separations

by thermolysis

[MeC,H,Mo(CO),l,,

and

of reactants.

group

A complex

short

easy

An X-ray

prepared

as a 1,4-bidentate

conformation.[5201 (2931.

is very

is a mixture

oligomers.IS191

[Mo(COl,(PhAs),l. behaving

n = 6

boat

ligands has been

and

formulated

as

Ph I CP

/*"\

Cp>Ti\;;/As\Ph

(294) (293)

Cp"Mo(CO),('13-As~l.

C~'MO,(CO),(~,~~-AS,)

cis-[Cp"Mo(C0)(~,~2-As,)l,. heating

with

arsenic

is probably analogue been

[Cp"Mo(COl(P,llz

in toluene

at

As606

ring

plane

of six oxygens

three

arsenic

arrangement

both

whose

The

on long third

compound

(293) and the phosphorus

complex

oxygen,

150°C give

containing

[Mo(CO),l,(AsMel,o takes

[Cp"Mo(COIJla

at 14O"C.[522]

with

of dissolved

[Mo(COl,l,(MeAsO),, and

and

from

with

two Cr(CO),

groups

has

investigated.

In the presence (MeAs),

in xylene

isostructural

structurally

result

a stabilised

of a flattened

sandwiched These

to the molybdenum

between

then

and

cycle-hexa-arsoxane, The twelve

cube-octahedron two planes

coordinate

atoms.

of Mo(CO),

of a complex

as a byproduct.[5231

the form

atoms.

solutions

crystals

each

membered with

a

containing

in a facial

Treatment

of

(PhAs),

with

107 CpzTiClz the

in

the

moderately

presence air

stable

contains

normal

As-As

(109.5”)

is

largest

substituted

mol

(2961.

of of

one

either

but

with

magnesium

complex,

bond

metal

but

if

(MeAs),

bond

is

promoted

PCl,.

Br,,

or

I,

of

the

mols

Me

to

give

reagents

methyl

starting

material.

treatment the

of

(2951

with

dihalides

yields

of

Me

A&s

of

angle

related

the

on

yields which

As-As-As

The is

As-As

two

good (2941

the

known.[5241

results

gives

Cp,Ti(AsPh),.

distances

yet

compound

Cleavage one

the

of

Me

X- Ams-X

X-AflTsxz As

As

X (295)

(296) (297)

MeC(CH,AsX,lJ that

are

these

The

are

structures

of

in

3 and

shown

Figures

five-membered when

poor.[5251

products

of

potassium

then

gave

phases first

in

the

reaction

from

150°C.[5281 During

of

Arsenic-tin attempts

elements

corner

a mixture

in

a

to

AsloTeJZ-

linked the

to

P,,3-,

used

for

mixture data

show

rubidium

atoms

symmetry

consists

ethylenediamine

the and

A number

presence

of

complex of

of

a

binary

and

a

is

arsenides

obtained

structure

the

between

chains

and

8 unit related

lit

257.2

be heated

and

to

263.8pm.

from

the

compound

from

anions. (As-)

ratio

polyarsenides

obtained

bicyc phase

can

5:2:6

niobium

anionic

shaped

are

sharing

ethylenediamine with

containing

[NbAs,13-

crown

AsllTeSedge

tetrahedra in

fall

novel

was

in

SnAs,

rubidium

the

[Rb(2,2,2-cryptl],[Rb(NbAs,)l reaction

six

the

in

K1.6As,.6Te

elements

distances

tube,

and

of

A tin-arsenic

synthesise

niobium

suggest

(2971.

consists

prepared of

however

ethylenediamine.15261

salt

again

second,

containing

isolated

atom.

spectra tetrahalides

N[(CH,),O(CH,),O(CH,,2lsN.[5271

Ca,Sn,As,,

X-ray

the

structurally

with

from

n.m.r.

Zintl

reacts

The

‘H via

The

related

resulted

cryptand

new 4.

Ph,PBr

determination. solution,

two

rings,

As,Te,

Addition

formed

a

solution

the

of

containing The

the

cryptand.

latter

and

a

alternate with

central

compounds,

D,, Nb(V)

108 including

SrPtAs.

have

been

also

Two views anion

by permission Sot..

SrPt0.70AsO_90,

BaPtAs.

BaPtAs,

As0 )

3.

As , oTe3Z-

BaPtSb,

synthesised.[5301

As(Z)

Figure

SrPtSb,

Chem.

of the

Figure

(reproduced

from

J. Chem.

Commun.,

4.

The As11Te3-

(reproduced J. Chem.

(1987)

anion

by permission

Sot.,

Chem.

from

Commun..

(1987)lQOl.

196).

5.3.2

Bonds

to Boron

Four-membered (mesityl)AsLi,

AszB, with

or Gallium units

RBCl,

methylpiperidino.[l421 were

discussed

Hydrogen

are formed

where

dimeric

in section

is evolved

from

analogous hedral

their

when

product)

CaI,-

hand,

dimethylarsine

and

to give

or 2,2,6,6-tetraphosphorus

reacts

Me,AsGaX,,

spectra.[5311

the product

containing

anions

of

compounds

5.2.2.

vibrational

on the other

R = mesityl

The corresponding

(X = Cl, Br or I) in a vacuum

Ga,14.

in reactions

With

slightly

[Me,AsAsMe,Il+

solid

which

is Me,As,GaI,

discrete,

the novel

with

Ga,X_,

are probably

Me,AsI

and

(Inz14

gives

distorted, cation

(As-As

242.7pml. The

silylmethyl

substituted

arsine

(Me,SiCH,),AsH

an

tetra-

and Ph,Ga

109

eliminate

benzene

symmetric

ring

and 253.0pm,

to

give

and the As-Ca-As

dimeric

(298)

following 85.08”.

with

important

a planar.

centro-

dimensions:

and Ca-As-Ca

Ca-As

94.92”.15321

251.8

Gallium

Ph,Ca -As(CH,SiMe,),

I

(Me,SiCHzJzAs

-CaPhz

I

(298) [(Me,SiCH,),Asl,Ca

trichloride the

ring

and is

Other

(Me,SiCH,),AsLi

distinctly

methods

sterically

for

and

(51)

RzAsLi

+ CaCl,

-t

R,AsLi

+ Me&aCl

2R,AsLi R,AsLi

synthesising

+ CaCl,

a dimer

summarised Rather

(299)

but

-t

here

particular

in equations unusually

(47)-

for

compounds

. . . (47)

+ LiCl

l/n[(R,As),CaCl), (R,As),Ca

in

+ LiCl

l/n(RpAsCaMe,),

+ (R,As),CaCl

R*AsSiMe,

are

(52).[535]

l/n(R,AsCaCl,),

-+

gives

arsino-gallanes,

products, and

-+

+ CaCIJ

also

non-planar.[5331

hindered

(50)[534]

-As(CH,SiHe,),

. . . (48)

+ 2LiCl

. . . (49)

. . . (50)

+ 3LiCl (R,As),Ca

-+

+ Me,SiCl

. . . (51)

+ Me,SiCl

. . . (52)

R = mesityl R=AsSiMe, of

this

gallane from

+ CaC13 type, is

l/n(R,AsCaClz),

diffraction

monomeric,[5341

detailed

trisubstituted treating

X-ray

-t

the

n.m.r.

and the

spectroscopy

arsino-gallane. trichloride

shows

with

that

dimer is

tris(dimesitylarsino)~[(Me,SiCHz),As12CaC1),,

fluxiona1.[5351 can also

Ca(AsBu*,),, three

mols

of

Bu”,AsLi,

A monomeric be obtained but

a cyclic

by

110 dimer,

(R,GaAsBu",l,.

reacts

successively

butyl

similar with

is produced

1298) -1

and two mols

when

of either

CaCl, methyl

or

lithium.[l471

A novel

cluster along

obtained,

in a reaction analysis

Figure

compound

with

PhAsH,

structural

Chem.

5.3.3

Bonds

Arsenic(III1 containing outlined

has been (PhAsl,,

X-ray

(Me,SiCH,),Ca.[5361

details

are shown

in Figure

5.

cluster

[(PhAsH)(R,Ga)(PhAs),(RCa)41

where

Commun..

to Carbon

by permission

R =

from J. Chem.

Sot.,

(198614871.

or Silicon The

an arsenic-carbon in equation

core

including

is ~(PhAsH)[(MeSSiCH21&al(PhAs),-

(reproduced

Compounds.

products

of the organogallium-arsenic

compound, Me,SiCH,

an As,Ga,

of other and

the compound

Structure

5.

containing

a range

between

shows

(Me,SiCH,Gal,l;

GCOCl

to

Bu",AsLi

first triple

compound bond

(mp. 114-6°C)

has been

synthesised

as

(53).[5371

LiAs(SiMe,l,

~~C
. . . (531

111

The

fluorinated

thermolysis a range

C

CF,-As=CF,,

(Me,Snl(CF,l,As,

prepared

undergoes

of 1,3-dienes

(Diels-Alder

including

(300)-(303).[5381

compounds

I

of

arsapropene.

in situ

by

[2+41 cycloadditions

adductsl

giving

a series

Arsa-alkenyl

Me

with

of new

transition

Me

CF,

I

CFz

As-CF,

I

\ 85

As-CF,

CFz

I

As-CF,

(303)

(302)

metal

complexes,

mesityl

can be obtained

Cp(COl,FeAs(SiMe,l, compound double

contains bond

A series

Cp(CO),Fe-As=C(OSiMe,)R,

e.g.

or CeH,But3,

with

RCOCl;

a short

As-C

where

the structure bond

R = But,

by treating of the t-butyl

(182.lpm)

in keeping

with

the

character.[5391 of methylarsine-boron

1-3. X = Cl or Br, has been

adducts,

prepared

and

Me,AsH,_,.BX,, 'H n.m.r.

for n =

data

obtained.[5401 1,3-Bis(diphenylarsino)propane, with

hydrogen

be reduced heterocycle aqueous

iodide

by sodium

gives

in THF to give

hydrogen with

tricyclic

(3051.

peroxide

Treatment

aqueous with

bonded

chlorine

groups

and the compound

adduct

of N(CHzCH,AsI,l,(CH,CHMeAsIzl

ammonia

Ph,AsNa

in THF

replaces

by

the

the covalently

converted

by benzene

can

and

gives

in ~HN(CH,CH,Cl),(CH,CHMeClllCl can be subsequently

which

sensitive,

can be oxidised

to (HO),As(O)(CH,),As(O)(OH),

concentrated

atoms

on treatment

tetraiodide

the red, air

The tetraiodide

(304).[5411

treatment

Ph,As(CH,l,AsPh,,

the corresponding

by AsPh, to an HI

elimination

with

112

Ihs

H

(CH,l,Cl 'c'

S'

hydrogen

compounds

are

formed

on treatment

i ne.

used

as

S

react

somewhat

longer

trifluoromethyl Reaction

of

which

is reduced e.g.

salts

contains

also

derivative series

or H,S

including

(-1.

were

of reactions.

PhAs(SiMe 3 ) z and PhP(SiMe,), and P-C(O) but similar

normal

[(Me,Sil,CHlAsCl

to metallic

both tin,

with,

butyl

lithium have

e.g.

with

lithium

as a strong

distances

giving

of 205 and

to those

An alternative and both

As,Li,

and a nitrogen

centred

route

in

from Ph,AsH:

ring.15451

analogue

e.g.

SnCl,

nucleophile,

lithium

and the second

Related and

the trimer

it is converted

to such

Li(dioxanl,AsPh,

prepared

gives agent,

HCl or MeCl,

[Li(l2-crown-4112[SbPhZ].HTHF

obtained

metal

reducing

and as an arsenic

respectively,

been

a four membered

4l,][Sb,Ph,].THF, were

in this

ammonia

chlorides,

the As-C(O)

or R,AsMe.[5441

uses

aqueous

alkyl

than

can behave

[Li(Et,Ol,AsPh,]

compounds,

both

for two

derivatives.[5431

on treatment

to R,AsH

materials

as a precursor

for X = 0 or S, which

respectively,

substituted

with

in which

PhM[C(OlBu*l,

(3071.

serves

and the trithiahexane

tarting

will

with,

Other

,JCl

IHN(CH,CHMeCl

Bu"COC1

compound

[N(CH,CH,l&H,CHMel,(As4X4),

in triethylam

191pm.

This

iodide.[542

new

also

's

product

antimony

[Li(l2-crown-

[Li(l2-crown-4lNPh,l

113

/

Li

Iis \

Li

I

I As[CH(SiMe.l3 2 I 2

[(Me,Sil,CHI,As 'Li/

(THF) But \As

/Li\As,AsBurz

Bu" z As'

'

Li/

'Bu'

(THF)

In what

must

anhydrous ring and

arsenic t-butyl

yields bond

be a highly

magnesium atoms

on treatment

trimethylphosphine

the dimer

to two

groups.[5461

dinickel with

reaction,

gives

coordinated

and Bu',As

an unusual

complex

bromide

lithium The

complex

Bu',AsLi (3081,

NiCl,(PMe,l,:

atoms

(As-Li

same arsenic

(3091 with

can be displaced

with

containing

a direct

25Bpml

reagent Ni-Ni

the coordinated with

p-tolyl

isocyanide.

[5471

AsANi\ I

Bu’

2

\Ni/AsBu*Z

Fe

iMe, As

(3091

Bromine

substitution

is treated with

with

takes

place

Ph,AsNa,[5481

and,

PhAs(SiMe,l,

Me,SiCl.

6

reaction

leads with

to a redox the cobalt

when while

(311)

trans-WBr(COl,(bipylCNEt, treatment

process chloride

giving complex

of FeCl,(PPh,l, iron, gives

(PhAsl, a green

and

114 solution

from which

can be

isolated

As),(~,,t~3As,)(PPh,),1.[5491 tetrahedral and

one

Co,

face

coordination of this

three

faces

to an As,

ring.

The

of a Ph,P

reaction

The compound

with

cluster,

linked

the cobalt

group

is that

to each

As-Ph

cluster

contains

capped

a

by !J,-As ligands

structure

cobalt.

bonds

[Co,(V,-

is completed

An unusual

are broken

by

feature

at room

temperature. Co-condensation n6-arsabenzene ferrocene arative

route

Freshly

to

monomeric solid

and Ph,AsO,

during

slightly

bent.[5531

solution

give

Compound

species,[5521

an

investigation

the product

structure,

with

arsaprep-

1,4-dichloro-1,3-

and

follows

iron

by

chloride.

INCO add oxidatively

to

and M = As, Sb or Bi. to

but for Ph,As.I,, of reaction

contains

Triphenylarsine

a compound

to the

an efficient

(3101 then

or 4-FC,H4

leads

and the parent

lithium

of IN, and

4-Cl

atoms

following

(3111 from

(3111 with

solutions

Ar,MIX

iodide

ionic

of

Ar = 4-Me.

purple

Ph,P

isolated

1-phenylarsole

prepared

and chromium

(C,H,Asl,Cr.[5501

has now been

reaction

where

has an

ligand

and PhAsLi,.[5511

successive

give

complex,

(-1

butadiene

Ar,M.

of the

and

iodine

[(Ph,AsI),I,II,,

as a

of manganese(I1)

an As-I-I

the stoichiometry

isolated

system

which

is

in dichloroethane Ph,As.21,,

which

like the corresponding

product.[2261

Elementa

arsenic,

antimony

mercurials

C,X,Hg13

where

(3121.1554 1

or bismuth

on treatment

with

phenyl

X = H. F or Cl g .ve the heterocycles

115 Arsenic(V)

Compounds.

two-fold

axis

trigonal

bipyramidal

atoms

passing

(As-F

of

in

in

stable

ylid, points

ylidic

bond.

carbon

trifluoroacetic

initially

in

the

directly

compound

is

edge

situ,

an

and

a

bond

The

from

group

with

giving

fluorine

trifluoroacetate,

A crystal

order

of

ca.

1.6

gives

structure for

reaction

the

arsenic-

with

PhSAs:C(COCF3),

but

there

is

no

benzaldehyde.

The of

of

SiAs,

a

methylene

ethyl

corresponding

the

isotype

organic

antimony

generates with

yields

with

one

contains

positions.[5551

which

synthesis

sharing

(C,F,l,AsF,

about

PhLi

Compounds.

prepared

Si-As-Si

axial

to

reaction

Arsenic-Silicon

arsenic

with

anhydride

comparable

of

Ph,As:CHCOCF,.[5561

determination

of

through

MePh,AsI

triphenylarsorane new

structure

coordination

178.lpm)

Treatment

a

The

arsasilicate,

RbAs

in

elements K,SiP

a

as

Rb,SiAs,, quartz

red

(Si-As

reactor,

can

needles.15571

2 containing

tetrahedra

isolated

a

polymeric

238.lpm,

be The

chain

As-Si-As

anion

95.7”.

84.3”).

5.3.4

Bonds

to

Continuing

Halogens

investigations

trihalides

have

shown

hexaethylbenxene moisture

can

into

that be

a

between

In

coordination

of

two

the

AsBr,

arene

adducts

discrete

isolated,

sensitive.[5581

sandwiched

arene

2:l

which the

to

arsenic

of

only

slightly

state,

molecules

Group

complex is

solid

with

and

the

the

(As-centre

of

AsBr,

with air

arene

data

5

and

is

show

strict

Us

arene

316pm). Iodine(V)

fluoride

organochloro for

R = Bu,

arsenic state

is

a

derivatives Ph,

and

C&F,

antimony

fluoride

useful of

etc.,

for

agent

antimony

M = As,

reactants

except

oxidising

arsenic, Sb

yield

or

Bi

the

and

a

range

bismuth,

of

R,_,MCl, The

n = o-2.15991

appropriate

which

Ph,AsF,,

for

or

+5

oxidation

decomposes

to

Ph,AsF,

and

react

phosphorus(V)

AsF,. Trithiazyl oxide

but

chloride, with

identified of

as:

(S,N,)(BiCl,l

first Figure

61

heavier

(S 3554 N and

compound

cubane-type

the

N&&l,,

which

shows arises

As,C~,,~-

does

Croup

not

5 trioxides,

(As,Cl,e1.2S,N,.

octameric by

addition

species.

reaction

(S,N,l(SbC16)

(S,N4C111BiC1,1.[5601 an

with

anion of

with four

gives and

salts

mixtures

An

X-ray

study

S,

point

symmetry

AsCl,

molecules

on

to

the (see a

116

Figure 6.

Structure of the As,C1,e4

anion (reproduced by

permission from 2. Anorg. Allg. Chem., 537(1896)145). The low temperature form of H,O(AsF,I shows distortion of both the pyramidal cation and the octahedral anion through three independent O-H.. .F hydrogen bonds.[5611 In the solid state, AgF,.AsF, consists of octahedral AsF,- ions and infinite chain (AgF"), cations lying along the a axis (Ag-F 200.0pm. F-As-F 175.5").[5623

The chains are then cross linked via fluorine

bridges from AsF,

anions to give effective pentagonal bipyramidal

coordination about arsenic.

Of the six As-F distances, five which

involve bridging fluorines fall between 171.4 and 172.9pm while the single non-bridging fluorine forms a substantially shorter contact f167.7pm).

The compound is clearly structurally different from

SnF,.AsF,, which contains cyclic fSnF),3' cations.

Structures for the AsF, adducts formed in liquid sulphur dioxide solution with both benzo-2,1,3-thiadiazole

and benzo-1,2,3-thiadiazole

show

interaction via a nitrogen atom of the ligand.15631 U.V. and p.e. spectroscopy point to the presence of AsCI,F, the least stable arsenic(V) chloride fluoride, in the gas phase over heated ~AsCl,IIAsF,1.~5641 and the compound has been isolated during sublimation of [AsCI,I[ASF~I in the presence of potassium fluoride.[5651 matrix

The related dichloride, AsC12F3, characterised by

i.r. and Raman spectroscopy, can be obtained from AsCl,F* by

halogen exchange with calcium chloride.[5661 5.3.5

Bonds to Nitrogen

The novel two-coordinate arsenic imide, ButJC,H,N.As:NC,H28ut,,

117 obtained

from

mentioned

in section

Multinuclear reactions

of Me,AsH good

where

MeAsH,

results which

suggest

initial

between

Me,AsNMe,

Me,AsAsMe,

to subsequent

unstable

substituted

between

and Et,AsAsNR,

decomposition

to give

occurs

as an

Me,AsAsEt,, Me=AsNR,

Coordination

only

the n.m.r. intermediate

products.15681 is probably

and Et,AsAsEt,

(Fl = Me or Et) but

symmetrisation.[5691

and BH,. THF apparently

other

in each

In cases

compound,

Me,AsAsMeH

diarsine,

of reactions

which

Me,AsAsMez.[567]

(MeAs 5 among

giving

product

been

to follow

and Me,AsNMe,.BH,,

for the dimethyl of

formation

used

has been

of the diarsine.

is substituted

An unsymmetrically the

spectroscopy

with

yields

decomposes

has already

5.2.5.[3021

n.m.r.

case

give

and But ,C,H,NHLi

the trichloride

results

between

at low temperatures

(Me,NBH 2 ) 2 and diarsines

or

point

Me2AsNRz

with

occurring

on

warming.15701 A new series

of aminoarsonium

chlorides

Me, Et, Pr or Ph and R' = H or Me,

[R,AsNR,'lCl.

results

when

R,As

where

reacts

R =

with

R,'NC1.[5711 Extending

reactions

arsenic(II1) Br or I point the expected

already

chlorides

to formation cage

reported

and K,SN,. of

substituted

with

(313) as a result When

structure.15721

AsX,. of SN,

the substrate

/

\

/N

N -As

between

reactions

\ (313)

H

Me H\c/R

,,.-As"\As-Bu' I N

I

As' yN\/Ny

\As

for X = Cl, loss from is a bis-

118 (chloroarsine), Me,

reaction

(3151

with

K,SN,

gives

or RCH(AsCl,),,

the novel

for R = H or

heterocycles

(3141 and

respectively.[5731

5.3.6

Bonds

Crystals with

MeCH(AsButC1),

e.g.

to Oxygen

of a tetrameric

a small

amount have

(mesityl),. dichloride

with

oxide

isolated

potassium

from

compound

As-O

hydroxide

179.0pm.

Bu",C,H,AsF,

product

hydrolysis

together

(mesityll,AsOAsof

(mesityllarsenic

in dimethoxyethane

The eight-membered (mean

[(mesityllAsOl,.

of a reorganisation

been

solution.[5741 conformation related

arsine

ring adopts

O-As-O

a crown Hydrolysis

98.9").

by the same method

however

of the

led to

(316).

Synthesis

of an arsa-aza-oxa

mentioned.[5421 cryptand.

cryptand

and the chromium

[N(CHzCH,),I,(As,O,),

has already

pentacarbonyl has been

been

complex

obtained

of a related

on reaction

with

Cr(COl,.THF.[5751 A barium

salt,

polyarsenate with

barium

considered to give are

Ba2Ash0,,,

anion oxide

has been and As,O,

as pairs

a series

further

condensed

arsenites.

Full

The

linked

AsloOlo

rings.

have

i.e. Na,(H,As,O,l.

structure

These strong

now been

can be

from

units

double

chains

(As...0

268pm)

published

NaAs0,.4H,O,

isolated

reactions

by As(OlOAs(O1

by relatively

structures

condensed

hydrothermal

chains

and Na,(HAsO,l(AsO,l.l2H,0.

system

a new highly from

at ZOO"C.[5761

(AsO,),

into sheets

bonds.

Low

isolated

of condensed

linked

secondary

5H,O

of

containing

for four

Na,(HAsO,).-

the Na,O-As,O,-Hz0

at 6"C.[5771 temperature

heating as AsaO,

arsenic(V)

matrix oxide

isolation

shows

in a vacuum

for n = 6-10.[5781

that

giving

1.r. spectra

oxygen

lower were

is lost on

oxides

formulated

interpreted

on the

119 basis

of an As,O,

bonds

which

Strong

absorb

hydrogen

stabilising basically an As-O

cage

the

at ca.

distance

complex

first

are also stable The

is important

in

and p-nitrophenol

(mean C-As-C

with

108") about

The hydronium

prepared

reaction

at 600°C)

in 1919,

arsenic

and

salt

is now known

and NaJAs7019.

system.[5811

for M = Li-Cs,

Sn(HAsO,l,

As=0

to be a

~H,0sl'~As~0,C,H~~~1~.~5801

in the Na,AsO,-As,Os MSn,(AsO,ls

of terminal

Na2As4011 (m.incongruent 67O"C), NaAs,O,

New compounds, (peritectoid

of Ph,AsO

geometry

of 166.8pm.I5791

of

number

IO... 0 255.5pm)

1:l adduct

tetrahedral

the required

lOZOcm_'.

bonding

H[As(0,C,H4),l.nH,0, dioxan

with

and ZMCl,

can be synthesised

heated

isostructural,

have

and the double

finally

been

from mixtures

to 6OO"C.[5821

crystallising

observed

tin arsenates, of

The compounds

in the space

group

R3c and

to 950°C. following

LiH,AsO,. obtained

arsenate

orthorhombic from

structures form,

concentrated

have

been

isostructural

aqueous

determined:

with

solutions

LiH,PO,

of LiOH

and

and arsenic

acid.[5831 partially

deuterated

PbCu(IlAs0, 1M acetic

T1HZAs0,,[584]

obtained acid

NaCu,(AsO,), 490K

for

edge

sharing

from a 1:l:l mixture

heated

hydrothermal

synthesis

a significant

100 days,

between

an AsO,

to significant

distortion

Na,Cu,H(AsO,l,

hydrothermal

copper

wire

at 493K

the corresponding bond

formulation

CuH,, (AsO,),, structure

from

shows

cross

tetrahedra,

for 7 days,

copper

NazHAs04,

Cu(OAc1,

of the structure and a CuO,

with

in

at

is common

square

Na,HAsOs.7H,0,

the compound

and contains

between

leading

NaNO,

is isostructural

a very

strong

two of the arsenate

and with

hydrogen

groups

so that

be Na,Cu,(AsO,),(AsO,HAs04).[587I aqueous

linked

from

Cu(HC0,12

and arsenic

distorted

by hydrogen

As,O,.

the structure

AgZn,H,(AsO,),

CuO and As,O,

polyhedra.[5861

synthesis

Jahn-Teller

AgCu,Cu(AsO,),.

feature

of both

phosphate

should

using

tetrahedron

for 48 hours,

(0.. .O 242.7pm)

of PbO.

to 4901(,[5851

AgNO,,

acid,

octahedra

the

and AsO,

bonds.[5881

CuS04.5H,0

is related

by replacement

CuO,

to those

of two hydrogen

and water of

at 300°C

AgCo,Hz(AsO,l,

atoms

and

by a further

atom.15891

As,V,O,,.

from a 1:2 mixture

24 hours,

the

structure

of AszO,

is best

and V,O,

considered

heated

as composed

to 833K

for

of close

120 packed

oxygens

vanadium(IV1

with

atoms

tetrahedral

four

the arsenic

synthesised

from

(NH,),HAsO,

in boiling

solubility

5.3.7 New

Bonds heat

quantities

water,

among

product

(2.1 x 10."

to Sulphur,

Selenium

and

data

other

are available

As,S,.[592]

From AsaS,

but a range

AsaS,,

As,.%

As,S,.

Transition

metals known

containing recently

has been

isolated

presence

of Cp"Co(CO),.[5941

behaves

molecules

and S, are found

and from

and determined

for B-As,S,,

Knudsen

over

P-AsaS,

of CalNO,)= properties

is

or Tellurium

experiments,

group

in

at 318K1.[5911

spectrometric

already

atoms

of hydroxyapatite,

of the vapour

are

different

and two arsenic(V)

analogue

stoichiometric

of formation

As,S,

AszS,.

sites

sites.[5901

Ca,,(AsO,),(OH),.

the

crystallographically

in octahedral

effusion

are the basic

of species

with

ASS=.

containing

of As4S4

The

As&,,

As,S,.[5931

stabilised

as a four electron

component

including

a compound

photolysis

As,S,,

and mass

ASS and As,S

in THF

structure

groups

an As,&

solution

group

in the

(317) shows

the As,S,

trisulphide

and Ph,PBr

donor.

_.--Br

Treatment in boiling

of a solution

Ph4P[M,SBr,l (318)

shown

Intermolecular antimony

ligands the

with

bonded

by the dotted interactions leading

products, diarsine

RetI),

Ru(II)

inter-

in the solid.

stronger

in the

dimers.

are obtained

when

[Me3PtXJ4

Me,As.S.AsMe,(sL).[596]

but binuclear

group

to

compound

lead to chains

to discrete

here

leads

intermolecular

substantially

fat-PtXMe,L,,

is a bridging

bromide

The arsenic

but

lines are

sulphide,

are unidentate

ligand

hydrogen

to Ph_,P[As,SCl,l

compound

Monomeric reacts

with

for M = As or Sb.[5951

is similar

actions,

of the appropriate

dibromomethane

can also

and Rh(III)

complexes be obtained.

complexes

have also

The (-1

in which Arsenic

been

obtained

121

/’ ’

Me,As

AsMe,

I ,X4

Me3Pt ‘x /PtMe3 both

with

this

ligand

dithioarsenate, corresponding

presence formulated

as

The

atom

and As,S

here

the three

investigated

membered

bonds;

and 242.5pm

As-Se

barium

compound.

(As-Se

230.3-232.9pm)

the As&Se,-PbS 325°C

5.4

with

in the

phosphorus

As&Se

metal

or As,Te

carbonate

P,Se atoms

units

but

distances

structures into

all

infinite salt

show chains

fall

of 234.8pm.

contains

and As&Se3

KAsSe,.H,O,

for the potassium

via

between

A related

isolated

AsSea3-

ions

C, symmetry.[6001

system,[6011 related

by three

The

incongruently

at 690K.

and SnAs&SeS,,

As,&-SnSe

for NiAs,Se,

complexes

X = Se or Te.15981

earlier,

AsSe 3 units

Se-Se

in the

P,, P,S,

Ba,AsSe,(OH).2H,O,

melting

solvated

where

new selenoarsenates,

distances with

5.2.7).[4941

as in the related

and CsAsSe,.HH,0.[5991

231.9

the

CofBF,1,.6H,O

to give

from an alkali

led to three

Se-Se

evidence

with

with

are disordered.

of pseudo-tetrahedral

PbAszSSes,

react

of the cyclic

rings

syntheses

have

RbAsSes.KHnO linking

is coordinated,

and the atoms

Hydrothermal 135°C

(see section

all

MeC(CH,PPh,),.

complexes

triphos

The

is isostructural

[(triphos)Co(As,X)l[BF,I,

from

at

and As,Te,

of triphos,

cobalt

Me,AsSMe.[5971

dithiophosphinate

As,Se,

As,Se,,

and with

Ph,Sb(S,AsPh,),

has been melting

system.[6021

from As&Se,-NiSe

There

phase

observed

in

incongruently

at

is also

studies.[6031

ANTIMONY Antimonides

5.4.1 Ten

new stibines

exchange

reactions

(R,SbMR'l

have

been

in the R,Sb2-R,'M,

and M = S. Se or Te;

reactions

investigated.[6041

Two of the compounds,

are

A similar

thermochromic.

stibine-bismuthine.

PriaBiSbMe,

with

characterised series

both

exchange

where

Ph,S,

reaction

were

also

and Et,SbTeMe,

produces

with

of

= Me or Et

and PhzSs2

Me,SbTeMe

in equilibrium

as products R/R'

the mixed

Pri4Bi2

and

122 Me,Sb,.[6051 Crystal

structure

(PhSbl,. S. where centrosymmetric

Sb,

ring

system

ring with

phenyl

The compound

angles

284 and 216pm

at antimony

isomorphous

or toluene groups

of 90":

Sb-Sb

Contributing

of rings

where

compounds

show a chair

shaped

in equatorial

has overall

respectively.

is the stacking

for the

benzene

S = dioxan,

positions.[6061 with

determinations

symmetry

close

to D,,

and Sb-C

distances

to the stability

the Sb...Sb

are of the

separation

is

420pm. An

intermetallic

phase,

Ba-,Ga,Sb,, can be prepared

elements

and has a structure

vertices

and edges

interconnected

274.lpm.

5.4.2

Bonds

to Carbon

on CaSb,

in edge

sharing

tetrahedra These

ribbons.[6071

into sheets

distances

in the vertex

Reviews and

further

Sb-Ca

contacts:

based

to produce

by long sharing

units

from

the

sharing

are

(329.6pml

Sb...Sb are 273.9

tetrahedra

and

266.9pm.

and Silicon

on organoantimony

chemistry

are available

19841608 I

for

1985.[6091

Good

yields

of mesitylhalogenostibines,

= Cl or Br and reactions

n = 1 or 2 can be obtained

between

In the presence

SbX,

(mesityll,SbSiMe, in air

and

(mesityll,Sb both

of Me,SiCl,

can be dehalogenated

former

(mesityl),SbX,_,

and

leads

to

(mesityll,SbOSiMe,.

itself

gives

(mesityl)SbBr,

the product

the distibine, is either

depending

and

in THF to give,

(mesityllSb(SiMe,l,.

(mesityll,SbBr

[(mesityl)Sbl,PhMe.

by reorganisation

at SO-100°C.[6101

(mesityll,SbBr

by magnesium

(mesityl)SbBr,

respectively,

Oxidation

of the

Dehalogenation (mesityll,Sb,

[(mesityllSbl,.PhH

on which

where

aromatic

is used

of

but with or in the

work-up.

\1 I

Ph,Sb-S

Treatment

of Ph,SbCl

with

the sodium

salt

of 8-mercaptoquinoline

.A.

123 in ethanol but Sb-N

gives

interaction

interaction also

(320)

Two

pyramidal

with

latter

the

from

and

Ph,Sb

about

bond

weaker:

and

becomes

in the apical

phenylantimony

from a reaction

anions,

with

In both

lithium

metal

compounds,

of BuLi

Sb...Sb

if this

is

distorted

position.[6111 [Li(l2-crownhave

with

been

PhzSbH

in the presence

the antimony

(244.4pml

significant

separation

antimony

group

is normal

[Li(l2-crown-41,1[Sb,Ph,l.THF

former

ether.15451

is much

a phenyl

containing

4),1[SbPh,l.HTHF

the Sb-S

by the 388.4pm

coordination

compounds

obtained,

(267.7pml

is indicated

considered,

square

in which

and the

of the crown

is in two fold

coordination. Although

the amine

obtained, were

related

derivatives,

reactions

unsuccessful

Et2SbNPhZ

designed

and gave

either

and Ph,SbNPh,

to give

R,'PPR,'

R,SbPR,'

can be

and R,SbAsRzl

or R,'AsAsR,'

instead.[6121 The

stiboranes,

PhSb(O,C,Cl~l.

obtained

benzoquinone. pyramidal

Ph,Sb(0,C,C141

have

position.[6131 both

with

4-MeCeH,(OzC4Me,lz, the antimony

geometry

requires

the same

form

a neutral

the presence

prepared

conclude

with

that

atoms

stiborane

Compound

but

(3211

of each

\

and pinacol,

pyramidal

rings

rings.

at antimony An attempt

//O \

Me

I 0-Sb-0 Me/'Me

diol

to in

to the salt octahedral

antimony

with

by donation

anion.16131

from

/

c-c

<

II C-CH l!l

in

oxygen

the

ato

second

complexes,

S-CH O\\

acid

apical

8-Quinolinato

group.16151

c-c

l!l

acid

from Me,Sb(OHl 2 and 2-thenoic

is widened

for

alternative.[6141

five membered individual

found

in

of square

a distorted

angles

//

pyramidal

bipyramidal

carboxylate

II HC-C

is also but

the stibonic

led instead

with

obtained

HC-S

and square

from Ph,SbCl 2 and 2,3-naphthalene

has a trigonal

one of the C-Sb-C

oxygen

in the

tetrachloro-

in the apical

geometry

stabilisation

of triethylamine

Et,NH[Ph,SbCl(O,C,oH,)1

chloroform

from

to the square

two unsaturated

donor

group

bipyramidal

with

bipyramidal

and Ph,Sb(O,C,H,-4-NO,)

is closer

(2,2'-biphenylenel-

reactions

trigonal

the phenyl

Trigonal

Ph,Sb[S,C,(CNl,I

The authors

via oxidation

respectively

geometry

and solvated

124 0

,0-&H&,-S

f

‘o-c

-_(CH,)2-S

L

1;

(322)

R&b&

where

with

R = Me, Et or Ph, are considered

essentially

spectroscopy

no chelation

but

the monosubstituted Hydrolysis

compounds,

R,Sb(O,SR')z

Ph. 4-MeC,H,;

CHzCH,OH,

R1 = Me. CF,.

from

(Ph,SbO),,

sulphonic

where

Me,Sb(OH),

or Ph,BiCO,

Vibrational

coordinate

covalent

the

showed

Sb-0

227.61228.0pm with and

distortion bridged

in apical

positions.[6191 but Sb-0

substantial 139.8

and

trigonal

ionic 136.5"

respectively

with

Triphenylantimony macrocyclic with

thioglycolic

Oxidation gives

oxide,

antimony

at 327.4

contact

for antimony causes

for the oxygen

with

groups

are

between gives

oxygen

atoms

formally

range

at the bridging

unexpectedly,

on

R = Ph or CF, show geometry

distances

acid

study

and short

and trifluoromethyl

stibine

sulphonic

Ph,M(O,SPh),,

Structures

Angles

ionic but five

by an X-ray

in the 225-237pm

carboxylates

of trimesityl

axial

in (321) above,

where

point oxygen

to are

derivatives 193 and

high

198pm.

yields

of the

(322. n = 1 or 2) on treatment

or B-thiopropionic

the dihydroxide.

group

The sulphonate

bridging

obtained

to essentially

compounds

bipyramidal

separations

Sb-0

point

as found

for the phenyl

been

is an addition

angles.

character.

have

of 210.61212.8

of one sulphonate which,

and the

and Ph,Bi(O,SR'),,

unidentate

There

[Ph,Sb(O,SRl,O

distorted

(Ph,Sb0),.[6171

was confirmed

and bismuth

of the equatorial

unidentate

with

distances

sulphonates

slightly

data

antimony

oxygen

of

and the appropriate

and Bi-0

for bismuth

and U.V.

in solutions

and Me,Sb(03SCH,CH,0H),

This

respectively.

a second 312.9pm

structures

remainder.

isostructural

which

gives

Ph or 4-MeCeH,,

for Me,Sb(O,SCF,),.2H,O

for the

n.m.r.

R = Me or Ph and R' = Me,

Me,Sb(0,SCF,),.2Hz0

structures

groups

from

is suggested

coordinate

R,SbClQ.[6161

CH,CH,OH.

acid.[6181

ligand

chelation

of Ph,Sb:C(SO,C,H,Me),

disulphonates,

where

by the

substantial

to be five

acids.16201

with

(mesityl),Sb(OH),

hydrogen which

peroxide with

in acetone

sulphonic

125 acids,

RSO,H for

compounds

formulated

determination

for

tetrahedral

as the

(189.4pml

character.

Addition

phenyl

gives

(3241.

16221

hydrogen

compound

yet

bonded

band to

isomeric

with

five

of

smallest

is

double

assigned

coordinate

the

Sb-0

appreciable

690cm.*

the

forms

distorted the

indicating at

addition A structure

indicates

antimony

observed

methyllithium

three

gives

about

An i.r.

of

(3231

CF,,

(mesityll,SbO.HO,SR.[6211

coordination

separation bond

R = Ph or

to tolyl

hypervalent

u(Sb-0). derivative

anion

lSb(tolyll,Me

Exposure bond.

to

to

oxygen

PhSb(SiMe,l,

and

5.4.3

Bonds

to

The

+3 Oxidation

isoelectronic of

lone

in

PhSb(OSiMe,l,

leads,

via

insertion from

into

State.

Calculations XeF,’ in

and

on SbF,2-

IF,

compounds

determining

the

point

overall

antimony(IIIl-antimony(V)

fluoride,

be

obtained

in

arsenic(III1

fluoride

solution.[6241

the

consists

of

croos-linked with

the

cation, SbF6-

structure three

of Full

moieties. structure

are

Evaporation acid

gives

SbF,

layers,

pseudo distances

that

it

of

solutions

crystals

of

similar of

of in

a three

forms

the

bond

or

interactions

the

eclipsed in

SbF,

dimensional, cation SbzFs3+

conformations

distances

as As shown

strong of

planar,

different

absence

this

and

units, SbF,

complex

discussed. of

trigonal

consists

details

SbF,.SbF,

Simplification

cations

Sb,F,+

either

which

(Sb,F,,),3”+

counteranions.

shows

types

solid

the

identified

can

diffraction,

reducing

the to

PF,

X-ray

Sb-Si

geometry.[6231

itself by

by

and

5SbF,.3SbF, with

the

respectively

Halogens

effects

A new mixed

air

Ph,Sb(OSiMe,l

Ph,SbSiMe,.[6061

TeF,-,

pair

the and

to

of

Mn(SbF,l,.2H,O those

bipyramidal 207.81211.2

MnCO, and in

with and

SbF,

shown

NaSbF,.[6251 axial

and

192.71192.6pm

in to

dilute contain The

equatorial respectively,

hydrofluoric infinite basic

unit

is

Sb-F but

three

126 further

contacts

number

An X-ray shows 322

in the range

structure

SbCl,

bonds

the third

that

in the pure

in three seven

As

complexes

at right

longer

which

sides

in other

trihalide. contacts, describes position.

polymeric, both

based

have

[SbCl,l.

been

overall

antimony

atom

oxygen

atoms

of the

and an open

!Me,Si),CHSb[W(CO),l,.

results

i.e.

from

involved number

the benzene

is

ligand.[6271

cluster

prepared

stibinidine

reaction

to

[P,OS,Cl,l

has been

structure

to

adduct

The antimony-iron

isolated.[6281

[629,6301

with

'-dimethyloxamide

and SbCl,.P,OS,Cl,.

ring

close

is also

of

two of

of the

geometry

bipyramid

[Fe,(CO),(~l,-Sb)I,[Fe,(CO),I

SbCl,.

type,

the coordination

a pentagonal

on bridging

of this

to the plane

raising

chloride-N.N

SbC1,.2POCl,

compound,

Each again

here

1:l antimony(II1)

giving

(SbCl,),.benzene

of the ring at distances

parallel

angles

in an axial

The

from

the coordination

complex.

on opposite

are effectively

with

and

raise

of the Menshutkin

molecules

and 330pm.16261

the Sb-Cl

ring

295-301pm

to seven.

complex,

of (Me,Sil,CHSbCl,

with

[W(CO),)"~.[6311 Compounds = O-9,

in the series

of methods

Crystallisation concentrated

shows

of

[Hpyl,[Sb,X,l,

bridging

chlorine

coordinated

have

bromine

All members

discrete atoms

of the appropriate to prepare

by hydrolysing hexachloride. of adventitious pyridine

nonahalide. the related

occupying

water

can also

in dichloromethane

three

isostructural

halogens

but these

structures, bridging

with

the

positions.

series by hydrolysis

but

it was

or tetramethylammonium salts.[6331

be obtained

of antimony(II1)

solution.

and

octahedrally

[Sb,Br,C19_,13~~

on solutions

antimony

can be prepared

cesium

[HpylJISb,C1,l

terminal

[Hpyl,[Sb,Br,Cl,_,l

the corresponding (Hpy)z[Sb,OCl,l,

each

in the

bioctahedral

n = O-6,

for

bridging

of the halogeno-oxydiantimonate where

by a

to give mixed

are again

and three

confacial

with

atoms

in [Sb,Br,Cl,13-

[Hpyl,[Sb,OBr,Cl,_,l,

possible

shown

of three

Antimony

terminal

prepared

investigation.[6321

structure

structure

octahedron

[Me,NlISb,Br,Cl,l

to three

C = Hpy and n

for X = Br or I. from

An X-ray

atoms.

and

and X-ray

was also

ribbon-type

by a distorted

[Me,Nl,[Sb,Br,l

compounds

acid

Hpy[SbX,Cl,l.

a polymeric,

surrounded

three

for spectroscopic

hydrochloric

tetrahalides.

where

or Cs and n = 3, 6 or 9, have been

C = Me,N

variety

[C'l,[Sb,Br,Cl,_,l"-,

from

not salts The

the action

chloride

The oxydiantimonates

and are

127 all

soluble

an

i.r.

in

a range

absorption

at

[HpylZISb,OBr,Cla_,l contain

discrete

bonding

atom

Cl,

one

(N...O

500cm-1.

with

n = 0,

2 or

anions

(3251

of

the

SbyCl

4.

of are

2-

Cl,

/Sb\Cl

characterised

these

compounds,

strong

cations

Halogen

are

isostructural

with

pyridinium

,CJ

and

Three

268pml.16341

Jib

cl/

solvents

ca.

Sbz0X,2-

between

oxygen

organic

of

and

,Cl

Cl ’

and

hydrogen the

disorder

1

by

bridging

occurs

\

in

both

,J

‘Cl’

2-

Sb\Cl I Ph

(3251 the

mixed

(3261

halides

uniquely

and

occupied

53% bromine

occupancy

Reduction addition

of of

slightly

pyramidal

intermolecular

Figure

7.

to

ining

shorter

about

antimony(III1

Structure permission 25(198618251.

of

the

with

[Sb,IlolAngew.

and at

iodides

[Sb,I,,I-

from

salt

only

Bridging

is

Sb-Cl leading

There

is

to

however

a

375.6pm. be

been

obtained

anion Chem.,

the

244.4pml

have

can

by

of

terminal

antimony.

contact

show

followed

(=1.[6351

310.3pml (243.2

Sb...Cl polymeric

sulphite

bipyridinium

anion and

are

positions

anions.

sodium the

positions

these

dibromide

coordination

new anionic conta

bridging

n = 4,

with

leads

substantially

square Three

the

(300.7

weaker first

for

IPh,Sb,Cl,l-

asymmetric

distances

the for

NH,[PhSbCl,l

bipyridine

centrosymmetric

although

by bromine

Int.

isolated. by treating

(reproduced Ed.

Engl.,

by

The

128 tris(dimethylaminolcyclo-propenylium antimony(II1) there

are

iodide

ranges,

275-282.

the structure

octahedra. from

with

antimony.[6371 interactions distances

Curious between

(18-crown-61-potassium

salt

Here

in square

X-ray

planar

in Figure

distorted

and SbI,, pyramidal

in this

final

structure group

anion

diffraction

coordination

results

cation

obtained

compound

shows

iodine

are the weak

of each

of a [Ph,Sb,I,lthe crown

to be

about

is an

with

7,

SbI,

and has a double geometry

compound

and potassium

solution.[6381

sharing

and a phenyl

The

of

into the three

(Ph,Pl,[Sb,I,1.2MeCN.

features

antimony

of 343-358pm.

Cr(COl,(PhSbI,)

anion

Ph,PI

mols

if all are considered

of edge

compound,

square

three

As shown

falling

and 337-349pm:

between

structure

contacts

is composed

second

interaction

bridged

Sb-I

298-311

The

with

in acetonitrile.[6361

18 independent

bonding

iodide

from

in THF

a central

to four PhSbI,

at

iodide

groups

(327).

The

+5 Oxidation

State.

1.r. and single

the

1:l addition

compound

of SbCl,

with

crystal

X-ray

Pr'N:C:NPr'

data

show

for

Sb-Cl

Ph

Ph

I /I ,SbL.

‘\‘/‘\ ISb\

l\Sb/llSb/l I 'l\I/l\I Ph

Ph (3271

distances

between

215.4pm.[6391

235.6

and 236.8pm

Complexes

of SbCi,

(R,_,R'PO).

or ethers,

solid

and dibromoethane

state

spectroscopy considered

and

exchange

SbCl,L

+ L'

law from

reactions,

;ti

have

SbCl,L'

'H n.m.r.

nitriles.

C,, point

solution

ionisation

to be less than

Ligand

rate

self

etc.

and an Sb-N with

3% from equation

oxides

in both

(45). follow

the

to i.r. and Raman

[SbC14.2LI'[SbC1,1~

12'Sb n.m.r.

is

spectroscopy.[6401 a first

order

. . . (45)

+ L

investigations

of

phosphine

symmetry

acording

to give

separation

in dichloromethane

or

129 tetrachloroethane

pointing

to

a limiting

dissociative

mechanism.[6411 Intercalation either

of

neat

or

period,[6421 is

also

SbCls

in

SbC15

which

possible and

is

not

trichlorides,

such

giving

and

1:4.5.[6431

products

Two new carboxylate containing

either

a hydroxy

from

the

as

(329, acid

synthetic is

R = CF, with

or

AlCl,, of

(328.

Et).

either

It both

have

1:0.16

also R = CF,

been

SbCle-MeOH

CaCl,

between

chlorides,

group

induction

graphite

BiCl,, ratios

antimony(V) methoxy

an

used.16431

into

SbCl,.

SbCl ,:MCl,

graphites

shows

when SbCl,F AsCl,,

with

bridged

bridge

and

solution

simultaneously

a bridging

carboxylic

natural

observed

intercalate

FeCl,,

both

tetrachloride

to

and

or

into

carbon

or

Et)

obtained

mixtures

or

SbCl,.H,0.[6451

Cl Cl

Cl

\ I

‘0’

I Cl

1 ‘Cl Me

Cl

I Sb

\

Cl’

1 ‘0’

Cl

charge

NOAsF,.C,Me, been

from

5.4.4

the

Bonds

The is

to

six

to

Sb(OMe1,

coordinated pairs

has

been

SbX(OMe1,

six

and of

possible and

consists oxygen

three

antimony

reorganisation

solutions

is

the

and observation

that

the

1y placed

sym etrical

almost

have

X-ray with

Oxygen by

of

dioxide

and

atoms.

structure

(198.6-201.2pml with

ring

is

NOSbF,.C,Me,

spectroscopy

results

NOSbCl,.C,Me,

2PhMe,

sulphur

optical

Among the in

NaSbCl-.

liquid

and

by n.m.r.

atom

respect

complexes,

obtained

diffraction.[6461 nitrogen

Cl

(329)

transfer

examined

I’Cl

H

(3281 Three

,

Cl

at

atoms

mixtures to

of

prepare

SbXZ(OMel.

Their

of

n which

layers

atoms,

three

longer

separations

forming

at

Sb,O,

Sb(OMe1,

and

members

of

i.r.

and

the

short

each

antimony

d i stances

(256.4-300.3pm1, By

rings.16471 SbX,, two

X = Cl mixed

Raman spectra

or

ligand show

Br,

it

series

130 structures

similar

SbX,(OMe) The new

there

negative

species

H,SbO-

ion mass

SbHzO-,

rather

stability

to that

are SbzX,

than

SbBe

have

been

heating lz'Sb

mixtures

the

both

molybdenum

calculations.[6481

determined

for both

the LJ and A isomers

cobalt(II1)

molybdenum

with

for which

available.[652]

Analysis

stretching

5.4.5 Good

from

dialkylamines

SbzO,,

Sb,S,

obtained. CHzCH,. from

SbF,

P-hydroxy

antimony(III1

of Sb,(SCH,CH,S),

that

of the arsenic

intermolecular

chair

were X =

prepared

rings

either

or by The in both

and additional

has already

The pentagonal been

structure

also mentioned are

e.g.

where

in ethanol

SbS,C,

can

derivatives,

compounds

been

at 347 and 350pm.

The PhsPISbzSBr,l

interactions

reaction

in chloroform.[6541

conformations

of Sb(S,PPh,l,

analogue

have

by

in situ

materials,

Sb,(S,Xl,

solution

(3301 shows

Sb... S bonding

structure

The

and only

structure

5.2.7.14931

of W(OMel,,

prepared

and B-cyanoethyl

tris(dithiolates1.

the dithiol

section

stretching

can be obtained

acids

starting

dithiolate

pyramidal

gives

for W-O

of the spectrum

and CH,CH,SCH,CH,,

half

the Sb-0

antimony(V)

and a sodium

and

both

that

to that

disulphide.[6531

Sb(OEt1,

intramolecular

give

dithiocarbamates

refluxing

the envelope

data

similar

dithiocarbamic

and PhSbO,H,.

and

antimony

or Selenium

with

CH,CH,OCH,CH,

data

a value

investigation

novel

Diantimony

by

and Sb,Mo,O,,

implication

are now

of these

with

occurs

although

methoxide

and carbon

to give

reduction

that

as +6 in Sb,WO,,

Sb,MoO,, the

from

Investigations

i.r. and Raman

of antimony(III1

the trioxide

be extended but

to Sulphur

yields

treating

pyrochlores,

tetramethylammonium

as 2.56Ncm‘'.

in a parallel

Bonds

with

of

reduced.[6511

of Sb(OMe1,

constant

show

tungsten

compound,

+3 and +5 antimony

[Me,Sbl[Sb(OMe),l

force

new oxide

oxides.[6501

with

as

di-IJ-(RR)-tartrato-

Four

spectroscopy

state

is partially

Reaction

formulation

its greater

level m.o.

and e.s.r.

corresponding

of the

of STO-3C

of the appropriate

Mossbauer

for

formation

for M = Mg. Ni, Cu or Zn, result

is in the +3 oxidation

contain

following

tetrahydrate.16491

Pb,[M,.,,Sb,.,,lO,.,,.

shows

but

rings.

for the former.

is preferred

bis(ethylenediamine)glycinato diantimonate(II1)

to Sb,O,

of Sb(OBu),

and Sb,O--;

HSbOH-

for the former,

in addition

spectrum

on the basis

Structures

of Sb(OMe1, rings

substantially

referred

is similar

previously stronger

to in to

but here leading

to

131 discrete

dimeric

units

(=).[5951

Br

\

-

the

‘Br

: ‘,’

I

\

jb/Br \Br

‘Br’

/

I 2-

SbHBLd

BY Br,;b,S

Br

Br (3311 Although

it

monoacetate

has is

PhSb(SAc1,

is

potassium

not

(mean

readily

Sb-S

interaction

pyramidal

coordination

completed

by

completing to

possible

compound Di-

and

and

and

dithiol,

be

for

bonding

is

via

square

state

structure

contacts about

and

Sb...O

distorted solid

Sb...S

isolation

(332, obtained in

X(CH&H,SH),

to The

via

PhSbCl*

(380pm)

antimony.

In

of

Ph,Sb(SAc)

has

not

the

instability

of

this

discussed.

trithiostibocanes can

between

coordination

reasons

are

thioacetate,

substantial

leading

formation

PhSb(OAc1,

Primary also

antimony.

possible

prepare

corresponding

metathesis

is

281pm

series,

PhSb(OAc1,

4-nitrophenyl)

by

octahedral

acetate

to

the

there

ca.

dimer

-

ethanol.16551

about

weak

the

in but

at

distorted

contrast

possible

known

obtainable

246pm)

secondary

proved

been

well

monothioacetate

sulphur

is

yet

however

the

X = 0 or

from

S and

RSbClz

presence

of

and

R = 4-tolyl

the

or

appropriate

triethylamine.[6561

The

0-J

R-S),___-e---X

d

‘S

(332) 4-nitrophenyl for

the

at

319pm

which

derivative

eight-membered but

raises

structural Ph,Sb(S,AsPh,),

there the

data

with ring

is

an

a

already

Ph,Sb(OSPPh,)

boat-chair

to

discussed

14951

and

conformation

Sb...S

intermolecular

coordination been

a

transannular

additional

antimony have

X = S shows with

six. for

interaction

interaction Preparative Ph,SbS,PPh,,[4941

Ph,Sb(O,PPh,).

and

132 A range

of substituted

R,Sb(SeCN),.

and

the oxygen

can be obtained

from

selenocyanate

trigonal Se-Se

5.5

bridged

contains

bipyramidal

at

including

and CeF,,

R,Sb(SeCN)OSbR,(SeCN)

halide

and potassium

18-crown-6.[6571 and pseudo-

pseudo-tetrahedral

units

by both

interconnected

obtained

Sb-Se

reaction

in a hydrothermal

and

of

llS°C.16581

BISMUTH

5.5.1

Dibismuthines

and Bismuthides

Tetra-i-propyldibismuthine insertion

into the Bi-Bi

or Te and exchange equilibrium

with

(p-tolyllaBi,, ammonia,

shows

p-benzoquinone (p-tolyl),.

Among alloys

obtained

from

the same

chalcogen

will

are

also Ph,S,

atom

Na[CpFe(C0),1,[6611

where

generated

with

is Sn,Bi,e-,

sodium

discussed

to an

in liquid above

and tellurium

by dissolving identified Bismuth

compounds

equivalents

[CpFe(CO),l,BiCl,

leads stable

but

analogues

X = S, Se or Te.[6591

two and three

or three

system

with

X = 0, S, Se

(p-tolyl),BiOC,H,OBi-

spectroscopy.[6601

in organometallic

chalcogens

and

insertion to give

and the selenium

clusters

chloride

product,

-Me,Sb,

(p-tolyll,BiBr

insert

in ethylenediamine

bismuth(II1)

free

Pr'=Bi-X-BiPr',

Low temperature

(p-tolyl),BiXPh

the anionic

bridging

with

to give

in the Pr',BiBiPr',

by tin n.m.r.

first

reacts bond

Pr',BiSbMe,.[6051

With

the products

time

of

both

Sb-Se

has been

and Sb,Se,

4-FC,H,

species

the corresponding

in the presence which

bridges,

Cs,CO,

selenocyanates,

for R = Me, Ph. 4-ClC,H,,

Ph,Sb(SeCN)

.CsSbzSe4.

antimony(V)

alkali

for the

first

can behave

as shown

metal

as a

by reactions

equivalents

of Na[Mn(C0),1.[6621

is trimeric

(3331 while

the

[Fe(CO),Cpl,

clAB1\ Cl

[Cp(CO),FelzBi

I

I Bi[Fe(COl,Cplz \Cl/

(333) second

compound

chemically

[CpFe(COl,l,Bi

to give

can be decarbonylated

[CpFe(uz-COll,Bi.

The manganese

of

of

photoderivative,

The

133 IMn(CO),l,Bi. 110.3”

is

and

All

the

Bi-Mn metal

[Fe(C0141Zatom

is

Bonds

to

to

more

give

5.5.3

rather

Bonds

shows

to

contains

Figure

8a)

the

with

at

and

330.2

each

(BiClslP

with

Related

must

reactions

hydrolytically of

bismuth-arene completed Slightly both

the

protonated former,

been

R = Ph or

aryl

the

1:l

longer

group

can

Treatment

of

be

and

displaced

PhSBi

with

compound

previously

Ph,BiO,SPh,

mentioned

above.

from

solutions

and

in

octahedral

246.5

with disposed

of

distorted

six

sixth

symmetry,

two

position

(see

an Y- arene

above

and

contains

Figure

8bl

to

the

in

the

presence

of

aluminium

compounds,

AlBiCl,.A,

contain

arene

complexed 272pm

octahedral salt

to

and

three

on a

other

a bismuth

side

coordination chlorine

is

found salt

trigonally

distorted

for with

is atoms.

[BiCl,l”the In the

and

or

arrange-

The

units.[6681

the

ring.

however

dimeric

further and

the

A = toluene

4,6-dimethylpyrimidine-2(lHl-thione.[6701 is

of

chloride

bismuth

geometry [6691

the

a tetrameric

in which

a centrosymmetric BiCl,

three

chlorines

below

As a consequence

attached

(see

by

lying

be

contacts

to

further

adduct

also

which

The

molecules

occupied

molecule

centre.

mixtures

coordination

alternately

is

bismuth(III1

BiCl,

and 248.9pm.

the

to

of

(Me6C6).2(BiCls).[6671

bismuth

diethylammonium bismuth

p-tolyl,

R=BiO,SR

addition

rings

separation by

iron

group.[663]

hexamethylbenzene-toluene

unstable and

AlCl,-

has

where

on

DZ,

hexamethylbenzene. ment

1985

a second

in

inversion

unit

one a Bi,Fe,

by a Co(CO),

based

coordinated

crystallographic chloride

RJBi.

The hexamethylbenzene

unit

with

contains

diarylsulphonates,

sulphonate,

between

groups

is

of give

give

or

336.8pm.

sheets.

bismuth

and

(Me,&H,).BiCl,

at

B6-mesitylene

edge

and

291.6pm. reacts

[Co(COl,I-,

This

1984

products

sheets

atoms

and

107.5

Halogens

of

chlorine

give

the

of

formation

BiCl,

not

in mesitylene

former

with

Bi(O,SPh),.[6661

does

Reexamination chloride

for

conditions

p-tolyl

but

but

Bi-Bi

acid

reactive

trioxide

reported

288.4

106.9,

when Bi,Fe,(CO),

,,I’-

Reactions

impure

sulphur

of

Carbon chemistry

an arenesulphonic

under

between

retained

on the

reviewed.1664,6651 with

angles

[BizFe,Co(CO),,l-.

bridged

Organobismuth

Mn-Bi-Mn

falling

are

[Bi,Fe,(CO)

giving

tetrahedron,

with

distances atoms

giving

lost

5.5.2

pyramidal

coordinated

to

three

in

134

Figure

a) Section

8.

showing

of the structure

a (BiCl,),

mesitylene circles)

groups

bismuth The by

atoms

chlorine

(258.3pm)

neither active

case

but hydrogen

thought Face

to cause sharing

terminal present

Bi-I

identified

in a DTA and system,[6721

5.5.4

rich

Bonds

Refinement corresponding

of the bismuth (reproduced

distant considered

with molecule.

atoms

generated

by permission

25(1986)7571.

(289.2pm)

chlorine

atoms;

in

to be stereochemically

less tightly

[Bi21913~~ units

of 316.9-327.7

bound

chlorines

with

bridging

and 293.4-303.2pm

in a peritectic X-ray

powder

and the

is formed

iodides

arene

is

and are

(Et,NH,),[Bi,I,J.[6711

decomposing

the bismuth

each

the distortion.

distances

incongruently,

and below

to the

The (filled

the sheet.

Int. Ed. Engl.,

more

bonding

BiBrJ-BaBr,

bismuth

Chem.,

lone pair

above

in (BiCl,l,.(Me,C,l

is not shown

bioctahedral

in solid

BaBiBrs,

above

and three

is the

of the sheet.

(open circles) unit

environment

inversion

from Angew.

close

section

are alternately

and below

bl The tetrameric

of BiCl,.(Me,C,H,l

reaction diffraction

related

qt 184°C. study

of

Na,BiI,

melting

from NaI and BiIs.[6731

Three

formulated

as Bi4_,I,

section

of the Bi-BiI,

Bi ,.,I

has been the

lower

and BiI are formed

system.16741

to Oxygen of the BiOBr chloride,

structure

the compound

indicates belongs

that,

as for the

to the PbFCl

layer

in

135 family

of

232.5pm

structures:

and

Bi&eO,

to

bromine

crystallises

infinite

[Bi,O,l”+

infinite

(Ge0,1,2n-

tetrahedrally to

contacts

within

381pm.

bonding prismatic Single

from

in

dimeric

section

and

and in

group to

five of

Cc and

the

a axis

fact

account

for is

long

the

two

a total

of with

short of

six

is

extended

12% of

oxygen

the

bismuth

as

trigonal

considered

contacts.

a new phase

formulated

as

mixtures

2Biz0,

V,O,.[6771

of

at

are

distance

ca.

best

oxygen

alternating atoms

forms

are

if

to

consists

germanium

there

others

bismuth

contacts

bismuth

226pm1,

additional

molten to

while

five at

forms

The

but,

latter

and

Bi_,V,O,,

have

been

Sulphur

structure

of

5.2.7.[4931 acid

in

is

bismuth

Bi(S,PPh,),

has

On coordination

dithiocarboxylic which

space

parallel

coordination

Bonds

The

the

(218

261pm

crystals

5.5.5

317.0pm.[6751

in

chains.[6761

oxygen

with

atom

at

layers

The and

isolated

bismuth

coordinated

contacts to

the

(334)

loses

surounded

to

a proton

by three _

already

been

discussed

bismuth(III1, giving

sulphur

the

a tris

atoms

complex

at

261.7-

NHEt CSSH

(334) 264.7pm

and

Nitrogen

is

contact

at

as

obtained

from

The

highly

reacts

with

leading axial shorter

and

leads

at

coordination

to

weak

rich

atom

distorted

positions Bi-S

A europium(II1

are contacts

a further

Bi...S

Complexes have

been

thio1.16791 anion

shows

two

coordinated

[BizS,,14solution

by two

chelating

pyramidal by the

basal

Eu,.,Bi,S,.

linked

geometry S e chain Bi-S has

when BiCl,

in acetonitrile.[680]

atoms

square

(268.3pml:

results

bismuth

occupied

compound,

but

[Bi(SC,H,NH,l,]

an ammonium polysulphide

each

296.3-310.8pm.[6781

dimerisation. and

2-aminobenzene

structure

to

sulphurs in

[Bi(SC,H,NH,)Cl,l sulphur

unusual

chain

further involved

368.9pm

formulated

The

three not

by an L2-

SL2about

which

chains bismuth.

forms

distances been

obtained

are

The

the 281.7pm. from

136 either

EuS and Bi,S,

3S at the same

mixtures

at

temperature.[681]

1073K or mixtures The bismuth

octahedrally

coordinated

(Bi-S 252-363pml

coordination

at europium

is described

prismatic.

Bi-S

together

with

and bi-capped Pb,In,Bi,S,, pyramidal

both

octahedra

are also

tetrahedral

trigonal contains

units.16831

prismatic both

atoms

while

2Bi and

are

the eight

fold

as bicapped-trigonal present

and octahedral PbS,

of EuS.

in Pb,In,Bi,S,, Ins, units

units.I6821

Bi.Sh octahedral

and BiS,

The

and monorelated

square

137

REFERENCES 1 2 3 4

10 11 12 13 14 15 16 17 18

19 20 21 22 23 24 25 26 27 28 29 30

H.F.Klein. H.Konig, S.Koppert. K.Ellrich and J.Riede, Organometallics. 6(1987)1341. M.j.Camenzind, B.R.James. D.Dolphin, J. Chem. Sot., Chem. Commun., (1986)1137. M.Midai, S.Aramaki. K.Yashida, T.Kodama, T.Takahashi, Y.Uchida and Y.Mizobe. J. Am. Chem. Sot.. 108(1986)1562. A.J.Bannister, M.I.Hansford and Z.V.Hauptman, J. Chem. Sot., Chem. Commun., (1987163. R.Bambal. H.Fritz. C.Rihs, T.Tschamber and J.Streith, Angew. Chem.. Int. Ed. Engl., 26(19871668. C.Gattow and S.Lotz, 2. Anorg. Allg. Chem., 533(1986)99. G.Gattow and S.Lotz, 2. Anorg. Allg. Chem.. 533(1986)109. B.Fusser and R.Mattes. 2. Anorg. Allg. Chem., 547(1987)158. O.Graalmann, U.Klingebiel and M.Meyer. Chem. Ber., 119(1986)872. A.Taeb. H.Krischner and C.Kratky. Z. Anorg. Allg. Chem., 545(1987)191. H.Krischner. F.A.Mautner and C.Kratky, 2. Anorg. Allg. Chem.. 533(1986)191. P.Charpin. M.Lance, M.Nierlich, D.Vigner, J.Livet and C.Musikas. Acta Crystallogr., C42(1986)1691. G.Persey and J.Wirz, J. Am. Chem. E.Leyva. M.J.Platz, sot.. 108(1986)3783. and C.Wentrup, Angew. Chem., Int. Ed. M.Kuzaj, H.Luerssen Engl., 25(1986)480. H.Bock and R.Dammel. 2. Naturforsch., Teil B. 42(1987)308. H.Bock and R.Dammel, 2. Naturforsch., Teil 8, 42(1987)301. A.Hassner and M.Stern, Angew. Chem., Int. Ed. Engl., 25(1986)478. C.Wentrup, S.Fischer, H.-M.Berstermann, W.Kuzaj, H.Luerssen, K.Burger. Angew. Chem., Int. Ed. Engl., 25(1986)85. A.Padwa. J.R.Gardaska. M.Tomas, N.J.Turro, Y.Cha and I.A.Gould. J. Am. Chem. Sot., 108(198616739. J.Beck and J.Strahle, 2. Naturforsch.. Teil B. 42(1987)255. D.J.Brauer. H.Burger, M.Grumwald, G.Pawelke and J.Wilke. 2. Anorg. Allg. Chem.. 537(1986163. F.J.Hofmann and H.Riffel, 2. Anorg. Allg. E.Allenstein, Chem., 534(1986)5. E.Allenstein. F.J.Hofmann and H.Riffel, 2. Anorg. Allg. Chem., 534(198617. E.Allenstein, F.J.Hofmann and H.Riffel, 2. Anorg. Allg. Chem.. 534(1986)13. W.Schwarz and E.Schrempt, Z. Anorg. Allg. E.Allenstein, Chem.. 546(1987)107. W.Eul and G.Gattow. 2. Anorg. Allg. Chem., 535f19861148. W.Eul and G.Gattow, Z. Anorg. Allg. Chem., 535(19861159. W.Eul, G.Kiel and G.Gattow, 2. Anorg. Allg. Chem., 535(19861167. W.Eul and G.Gattow. 2. Anorg. Allg. Chem., 536(19861119. W.Eul and G.Gattow. Z. Anorg. Allg. Chem., 537(1986)189.

138

33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49

50 51 52 53 54 55 56 57 58

59

60

W.Eul and G.Gattow. Z. Anorg. Allg. Chem., 538(19861151. W.Eul and C.Cattow, Z. Anorg. Allg. Chem., 543(1986)81. W.Eul, G.Kiel and C.Gatttow. Z. Anorg. Allg. Chem., 544(1987)149. W.Eul and G.Gattow, Z. Anorg. Allg. Chem., 545(1987)125. H.Grutzmacher and H.W.Roesky, Chem. Ber., 119(1986)2127. W.S.Sheldrick and P.Bell. Z. Naturforsch., Teil B, 41(1986)1117. K.Brink and R.Mattes, Chem. Ber.. 120(1987)351. K.Yamaguchi, T.S.Calderwood and D.T.Sawyer, Inorg. Chem., 25(1986)1289. W.P.Fang and C.H.Cheng, J. Chem. Sot., Chem. Commun., (1986)503. M.M.Doeff, R.G.Pearson and P.H.Barrett, Inorg. Chim. Acta. 117(1986)151. D.Littlejohn, K.Y.Hu and S.G.Chang, Inorg. Chem., 25(1986)3131. F.T.Bonner and N.Y.Wang. Inorg. Chem., 25(1986)1858. N.Y.Wang and F.T.Bonner, Inorg. Chem., 25(1986)1863. S.Ohba, F.Matsumoto. M.Ishihara and Y.Saito, Acta Crystallogr.. C42(1986)1. M.H.Barley and T.J.Meyer, W.R.Murphy, Jr., K.Takeuchi, Inorg. Chem., 25(1986)1041. F.Seel,C.Simon, J.Schuh, M.Wagner, B.Wolf, I.Ruppert and A.B.Wieckowski. Z. Anorg. Allg. Chem., 538(1986)177. W.W.Wilson and K.O.Christie, Inorg. Chem., 26(1987)1631. S.Kuwabata, S.Uezumu. K.Tanaka and T.Tanaka, J. Chem. Sot. Chem. Commun., (1986)135. B.Kamenar, D.Matkovic-Calogovic and A.Nagl, Acta Crystallogr., C42(1986)385. B.Ribar. A.Kapor. C.Argay and A.Kalman. Acta Crystallogr.. C42(1986)1450. R.Minkwitz. R.Nass and H.Preut. Z. Anorg. Allg. Chem., 546(1987)99. R.Minkwitz and R.Nass, Z. Anorg. Allg. Chem.. 549(1987)195. R.M.Kren and H.H.Sisler, Inorg. Chim. Acta, lll(1986131. C.Habben, A.Meller. M.Noltemeyer and G.M.Sheldrick, Angew. Chem.. Int. Ed. Engl., 25(1986)741. N.Wiberg, K.Schurz. G.Reber and G.Muller, J. Chem. Sot.. Chem. Commun., (1986)591. M.Hesse and U.Klingebiel, Angew. Chem., Int. Ed. Engl., 25(1986)649. P. von R.Schleyer and P.D.Stout. J. Chem. Sot., Chem. Commun.. (1986)1373. D.C.Anderson, A.J.Blake, S.Cradock, E.A.V.Ebsworth, D.W.H. Rankin and A.J.Welch, Angew. Chem., Int. Ed. Engl., 25(1986)107. U.Kliebisch, U.Klingebiel. D.Stalke and G.M.Sheldrick, Angew. Chem., Int. Ed. Engl.. 25(1986)915. A.Blaschette, E.Wieland. D.Schomberg and M.Adelhem, Z. Anorg. Allg. Chem., 533(1986)7.

139

61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77

;:

80 81 82 83 84 85 86 87

88

J.F.Richardson and N.R.M.Smith, Inorg. Chem., T.Chivers, 25(1986)272. S.Suzer and L.Andrews, J. Am. Chem. Sot., 109(19871300. L.Maya, Inorg. Chem., 25(1986)4213. H.Jacobs and C.Stuve, Z. Anorg. Allg. Chem., 546(1987142. B.Harbrecht and H.Jacobs, Z. Anorg. Allg. Chem., 546(1987148. and P.Paetzold, Z. Anorg. K.Stahl, F.Weller, K.Dehnicke Allg. Chem., 534(1986)93. U.Muller and K.Dehnicke, Z. Anorg. I.Schmidt, W.Willing, Allg. Chem., 545(1987)169. R.W.Cockmann and R.D.Peacock, J. Fluorine Chem., 30(19861469. C.Huttner and I.Jibril, J. Chem. I.A.Latham, G.J.Leigh, sot., Dalton Trans., (19861377. O.L.Hughes. I.A.Latham and C.J.Leigh. J. Chem. Sot., Dalton Trans., (19861393. J.Schmitte and K.Dehnicke, Z. Naturforsch., Teil B, 41(1986)793. and J.Strahle. Z. Naturforsch., M.Horner, K.-P.Frank Teil B. 41(19861423. Z. Anorg. Allg. H.Kohler, M.Jeschke and H.Wusterhausen. Chem., 549(1987)199. H.Kohler, H.Wusterhausen. M.Jeschke and A.Kolbe, Z. Anorg. Allg. Chem.. 547(1987)69. J.Beck and J.Strahle, Angew. Chem., Int. Ed. Engl., 25(1986)95. M.T.Nguyen and A.F.Hegarty, J. Chem. Sot., Chem. Commun., (19861383. W.W.Schoeller. V.Staemmler, P.Rademacher and E.Niecke, Inorg. Chem.. 25(198614382. M.W.Schmidt and M.S.Gordon, Inorg. Chem., 25(19861248. L.Zsolnai, C.Mohr, B.Sigwarth, H.Lang, C.Huttner, Chem. H.Weber, O.Orama and I.Jibril. J. Organomet. 304(1986)157. A.M.Caminade, F.El Khatib, C.Ades, M.Verrier, N.Paillous and M.Koenig. Phosphorus Sulfur, 26(1986191. A.-M.Hinke. A.Hinke. W.Kuchen and W.Honle, Z.Naturforsch.. Teil B. 41(19861629. Z. Anorg. H.Schafer. D.Binder, B.Deppisch and C.Mattern, Allg. Chem., 546(1986)79. L.Weber, K.Reizig and R.Boese, Angew. Chem., Int. Ed. Engl.. 25(1986)755. L.Weber and C.Meine. Chem. Ber.. 12Of19861457. L.Weber and C.Meine, Z. Naturforsch., Teil B, 42(19871774. A.H.Cowley. J.E.Kilduff, N.C.Norman and M.Pakulski, J. Chem. Sot.. Dalton Trans., (198611801. J.E.Kilduff. J.K.Leland, A.J.Bard. A.H.Cowley, N.C.Norman. M.Pakulski and G.A.Heath, J. Chem. Sot., Dalton Trans., (19871249. M.Culcasi. G.Gronchi, J.Escudie. C.Couret, L.Pujol and P.Tordo. J. Am. Chem. Sot.. 108(1986)3130.

140

89 90

91 92 93 94 95

96 97 98 99

100 101 102 103 104 105 106 107 108 109 110 111 112 113 114 115

Chem., J.Borm. C.Huttner and O.Orama. J. Organomet. 306(1986129. M.Yoshifuji, K.Shibayama, T.Hahisa, K.Toyota, J. Organomet. T.Niitsu, I.Matsuda, T.Sato and N.Inamoto, Chem., 311(1986lC63. S.Lochschmidt, C.Muller, B.Huber and A.Schmidpeter, Z. Naturforsch., Teil B. 41(19861444. Angew. Chem., Int. Ed. Engl., 26(1987)419. M.Baudler. and M.Peruzzini. Polyhedron, M.Di Vaira, P.Stoppioni 6(1987)351. H.Jacobs and K.M.Hassiepen, Z. Anorg. Allg. Chem.. 531(1985)108. H.Goldwhite. J.Kaminski. G.Millhauser, J.Ortiz. M.Vargas, and S.J.Smith, J. Organomet. Chem., L.Vertal, M.F.Lappert 310(1986)21. A.J.Ashe III and E.C.Ludwig Jr., J. Organomet. Chem., 303(1986)197. A.J.Ashe III and E.G.Ludwig Jr., J. Organomet. Chem., 308(1986)289. C.Charrier and F.Mathey, Angew. Chem., N.Maigrot. L.Ricard, Int. Ed. Engl.. 26(1987)548. M.Pakulski and G.J.Thomas, A.M.Arif. A.H.Cowley, Polyhedron. 5(1986)1651. M.Baudler and C.Kupprat, Z. Anorg. Allg. Chem., 533(19861146. M.Baudler and G.Kupprat. Z.Anorg. Allg. Chem., 533(19861153. M.Baudler and J.Simon. Chem. Ber., lZO(19871421. M.Baudler and D.Duster, Z. Naturforsch., Teil B. 42(1987)330. M.Baudler and B.Makowka. Z. Anorg. Allg. Chem., 528(198517. A.A.M.Demuth and W.Bauer. Z. Naturforsch., J.Ellermann. Teil B, 41(1986)863. K.Reizig. R.Boese and R.Benn, L.Weber, D.Bungardt. Chem. Ber.. 120(1987)451. R.Riekehof-Bohmer and U.M.Krause. Z. Anorg. M.Baudler. Allg. Chem.. 543(1986)45. J.Hahn and R.Riekehof-Bohmer. M.Baudler. U.M.Krause. Z. Anorg. Allg. Chem.. 543(1986)35. R.Riekehof-Bohmer and J.Hahn, Z. Anorg. Allg. M.Baudler. Chem., 544(1987)81. J.Hahn. R.Riekehof-Bohmer and M.Baudler, 2. Anorg. Allg. Chem., 546(198717. M.Baudler, R.Riekehof-Bohmer and J.Hahn. Z. Anorg. Allg. Chem., 547(19871149. C.Fritz. K.Stoll. W.Honle and H.C. von Schnering, Z. Anorg. Allg. Chem.. 544(1987)127. C.Fritz and K.Stoll, Z. Anorg. Allg. Chem., 539(1986165. H.-P.Stritt and H.P.Latscha, Z. Anorg. Allg. Chem., 542(1986)167. D.Duster and D.Ouzounis, Z. Anorg. Allg. M.Baudler. Chem.. 544(1987187.

141

116 117 118 119 120 121 122 123 124 125 126 127 128 129 130 131 132 133 134 135 136 137 138 139 140 141 142 143

O.J.Scherer, J.Schwalb, G.Wolmershauser, W.Kaim and R.Cross, Angew. Chem., Int. Ed. Engl., 25(1986)363. O.J.Scherer and T.Bruch, Angew. Chem., Int. Ed. Engl., 26(1987)59. M.Baudler, M.Michels. M.Pieroth and J.Hahn, Angew. Chem., Int. Ed. Engl.. 25(1986)471. E.Hey, M.F.Lappert. J.L.Atwood and S.G.Bott, J. Chem. sot., Chem. Commun., (19871597. M.Baudler and L. de Riese-Meyer, 2. Naturforsch., Teil B, 41119861399. C.Mujica, D.Weber and H.G. von Schnering, 2. Naturforsch., Teil B, 41(1986)991. V.Manriquez, W.Honle and H.G. von Schnering, 2. Anorg. Allg. Chem., 539(1986)95. W.Honle and H.G. von Schnering, Angew. Chem., Int. Ed, Engl.. 25(19861352. M.Baudler, B.Koll, C.Adamek and R.Gleiter, Angew. Chem., Int. Ed. Engl., 26(1987)347. M.Baudler and J.Germeshausen, Angew. Chem., Int. Ed. Engl., 26(19873348. M.Baudler, J.Hahn, V.Arndt, B.Koll, K.Kazmierczak and E.Darr, Z. Anorg. Allg. Chem., 538(198617. K-F.Tebbe and M.Feher, Z. Naturforsch., Teil B, 41(19863548. M.Baudler, R.Heumuller and J.Hahn, Z. Anorg. Allg. Chem., 529(1985)7. M.Baudler and D.Duster, Z. Naturforsch., Teil B, 42(1987)335. M.Baudler, D.Duster and J.Germeshausen, 2. Anorg. Allg. Chem.. 534(1986119. M.Baudler, R.Becher and J.Cermeshausen, Chem. Ber., 119(1986)2510. G.Cordier, H.Schafer and M.Stelter, Z. Naturforsch., Teil 8, 4lf198611416. B.Eisenmann, H.Jordan and H.Schafer, Z. Anorg. Allg. Chem., 532(1986)73. U.D.Scholz and W.Jeitschko, Z. Anorg. Allg. Chem., 54Ot19861234. Ya.F.Lomnitskaya and Yu.B.Kuzma, Russ. J. Inorg. Chem., 3lfl98611390. G.Wenski and A.Mewis, Z. Naturforsch., Teil B, 42(1987)507. A.Mewis, Z. Anorg. Allg. Chem., 545(1987)43. Ya.F.Lomnitskaya, Russ. J. Inorg. Chem., 31(1986140. R.A.Bartlett, X.Feng and P.P.Power, J. Am. Chem. SOC., 108f198616817. P.Kolle, H.Noth and R.T.Paine. Chem. Ber., 119(198612681. X.Feng, M.M.Olmstead and P.P.Power, Inorg. Chem., 25f198614615. A.M.Arif, A.H.Cowley, M.Pakulski and J.M.Power. J. Chem. sot., Chem. Commun.. (19861889. C.L.Wood, E.N.Duesler, C.K.Narula, R.T.Paine and H.Noth, J. Chem. Sot., Chem. Commun.. (19871496.

142

144 145 146 147

148 149

150 151

152 153 154 155 156 157 158 159 160 161 162 163 164 165 166 167 168

A.Haaland. J.Hougen. H.V.Volden, C.Hanika and H.H.Karsch., J. Organomet. Chem.. 322(1987lC24. O.T.Bleachley Jr. and L.Victoriano. Inorg. Chem.. 25(1986)1948. H.H.Karsch and A.Appelt, J.Organomet. Chem.. 314(1986)C5. A.H.Cowley. R.Geerts, R.A.Jones. A.M.Arif, B.L.Benac, J.M.Power and S.T.Schwab, J. Chem. Sec.. K.B.Kidd, Chem. Commun.. (1986)1543. T.Allspach and M.Regitz, W.Rosch, U.Vogelbacher. J. Organomet. Chem., 306(1986)39. R.Knebl, C.Heckmann E.Fluck, C.Becker. B.Neumuller, and H.Rittel. Angew. Chem., Int. Ed. Engl., 25(198611002. W.Rosch and M.Regitz, 2. Naturforsch., Teil B. 41(19861931. P.B.Hitchcock, M.J.Maah, J.F.Nixon, J.A.Zora, C.J.Leigh and M.A.Bakar. Angew. Chem.. Int. Ed. Engl., 26(19871474. J.F.Nixon and R.Mathieu, J. Organomet. M.F.Meidine, Chem., 314(19861307. R.Mynott, M.Regitz and W.Rosch., P.Binger. R.Milczarek. Angew. Chem., Int. Ed. Engl., 25(1986)644. M.J.Maah and J.F.Nixon, J. Chem. Sot.. P.B.Hitchcock. Chem. Commun.. (1986)737. S.I.Al-Resayes. P.B.Hitchcock and J.F.Nixon, J. Chem. sot.. Chem. Commun.. (19871928. M.T.Nguyen, M.A.McGinn and A.F.Hegarty, Inorg. Chem., 25(1986)2185. W.W.Schoeller and C.Lerch, Inorg. Chem., 25(1986)576. D.Conbeau and G.Pfister-Cuillouzo, Inorg. Chem., 26(1987)1799. Sulfur, R.Appel, V.Barth, W.Paulen and F.Knoch. Phosphorus 26(198611. B.A.Arbuzov and E.N.Dianova. Phosphorus Sulfur, 26(1986)203. A.Baceiredo, A.Igau. G.Bertrand. M.J.Menu, Y.Dartiguenave J. Am. Cem. Sot., 108(1986)7868. and J.J.Bonnet. H.Bock and M.Bankmann, Angew. Chem., Int. Ed. Engl., 25(1986)265. J.Crobe and J.Szameitat. 2. Naturforsch., Teil B, 41(19861974. K.Issleib. H.Schmidt and E.Leissring, 2. Chem., 26(1986)406. R.Appel. J.Menzel. F.Knoch and P.Volz. 2. Anorg. Allg. Chem.. 534(1986)100. O.Mundt. G.Becker. W.Uhl. W.Massa and M.Birkhahn. 2. Anorg. Allg. Chem.. 540(1986)319. B.Steger, H.Oberhammer, J.Grobe and D.Le Van, Inorg. Chem.. 25(1986613177. D.Gudat, E.Niecke, W.Sachs and P.Rademacher, 2. Anorg. Allg. Chem., 545(1987)7.

143

169 170 171 172 173 174 175 176 177 178 179 180 181 182 183 184 185 186 187 188 189 190 191 192 193

194 195

196 197

R.Appel and R.Moors, Angew. Chem., Int. Ed. Engl., 25(19861567. R.Appel. C.Casser. F.Knoch and B.Niemann, Chem. Ber., 119(1986)2915. C.Becker, W.Massa, O.Mundt, R.E.Schmidt and C.Witthauer, 2. Anorg. Allg. Chem.. 540(1986)336. J.Crobe, D.Le Van and J.Nientiedt, 2. Naturforsch., Teil B. 41(1986)149. D.E.Coons and D.F.Caines. Inorg. Chem., 26(1987)1985. A.Schmidpeter, K-H.Zirzow, A.Willhalm, J.M.Holmes, R.O.Day and R.R.Holmes, Angew. Chem., Int. Ed. Engl., 25(1986)457. B-L.Li and R.H.Neilson. Inorg. Chem., 25(19861358. A-M.Caminade, J-P.Majoral, R.Mathieu and Y.Y.C.Y.L.Ko, J. Chem. Sot., Chem. Commun., (19871639. C.Markl, H.J.Beckh, K.K.Mayer, M.L.Ziegler and T.Zahn. Angew. Chem., Int. Ed. Engl., 26(1987)236. A.L.Spek and A.J.M.Duisenberg, Acta Crystallogr., C43(1987)12161. M.A.McCinn and A.F.Hegarty. Polyhedron, M.T.Nguyen. 5(1986)1223. F.Mathey, Angew. Chem., Int. Ed. Engl., 26(1987)275. A.H.Cowley, Phosphorus Sulfur, 26(1986)31. A.M.Arif, A.H.Cowley and S.Quashie, J. Chem. Sot.. Chem. Commun.. (198611437. L.Weber. K.Reizig, M.Frebel. R.Boese and M.Polk, J. Organomet. Chem.. 306(1986)105. L.Weber, K.Reizig and M.Frebel, Chem. Ber., 119(1986)1857. H-U.Reisacher, B.Huber, C.Muller, W.Malisch H.H.Karsch, and K.Jorg, Angew. Chem., Int. Ed. Engl., 25(1986)455. and F.Knoch, Chem. Ber., 120(1987)125. R.Appel, V.Winkhaus R.Appel. J.Kochta and F.Knoch, Chem. Ber., 120(1987)131. and F.Knoch. Chem. Ber., 120(1987)243. R.Appel, V.Winkhaus and F.Knoch, Chem. Ber., R.Appel, V.Winkhaus 119(1986)2466. R.Appel. C.Porz and F.Knoch, Chem. Ber.. 119(1986)2748. J. Organomet. Chem., R.Appel. F.Knoch and V.Winkhaus, 307(1986)93. J-P.Majoral and J-C.Daran, R.Mathieu. A-M.Caminade, J. Am. Chem. Sot.. 108(1986)8007. M.Yoshifugi, K.Toyota. T.Niitsu. N.Inamoto, Y.Okamoto and R.Aburatani, J. Chem. Sec.. Chem. Commun., (198611550. Chem.. R.Appel. W.Schuhn and F.Knoch. J. Organomet. 319(1987)345. R.Appel, C.Casser and F.Knoch. Chem. Ber., 119(19861 2609. C.Markl, H.Sejpka, S.Dietl, B.Nuber and M.L.Ziegler, Angew. Chem.. Int. Ed. Engl., 25(1986)1003. W.Schuhn and F.Knoch, Angew. R.Appel, B.Niemann, Chem., Int. Ed. Engl., 25(1986)932.

144

198 199 200 201 202 203 204 205

206 207 208 209 210 211 212 213 214 215 216 217 218 219 220 221 222 223 224

P.P.Power and C.A.Sigel, R.A.Bartlett. M.M.Olmstead. Inorg. Chem.. 26(1987)1941. M.M.Olmstead and P.P.Power. Inorg. Chem.. R.A.Bartlett. 25(1986)1243. C.L.Raston and A.H.White, E.Hey, L.M.Engelhardt. Angew. Chem., Int. Ed. Engl.. 26(1987)81. S.Hietkamp and O.Stelzer, J. Organomet. D.J.Brauer. Chem., 299(1986)137. A.H.Cowley, R.A.Jones and J.M.Power. J. Chem. A.M.Arif. (198611446. sot., Chem. Commun.. W.Reich. A.Meyer and U.Schubert, K.Jorg, W.Malisch, Angew. Chem.. Int. Ed. Engl.. 25(1986)92. B.Sigwarth. U.Weber. L.Zsolnai, H.Lang. G.Huttner, I.Jibril and O.Orama, Z. Naturforsch., Teil B. 41(1986)191. Z. Naturforsch., J.L.De. D.Wolters and H.Vahrenkamp. Teil B, 41(1986)283. R.L.De and H.Vahrenkamp, Z. Naturforsch., Teil B, 41(1986)273. E.Leissring and H.Schmidt, Z. Chem., K.Issleib. 26(19861448. H.Schmidbaur and S.Schnatterer, Chem. Ber.. 119(1986)2832. S.A.Weissman, S.G.Baxter, A.M.Arif and A.H.Cowley, J.Chem. Sot.. Chem. Commun., (1986)1081. E.Lindner and G.A.Weiss. Chem. Ber.. 119(1986)3208. M.Pakulski and N.C.Norman, Polyhedron, A.H.Cowley, 6(1987)915. T-S.Chou, C.H.Tsao and S.C.Hung, J. Organomet. Chem., 312(1986)53. C.Heckmann, E.Fluck and P.Kuhn, Z. Naturforsch., Teil B. 42(1987)115. E.Lindner, C.Scheytt and P.Wegner, J. Organomet. Chem., 308(1986)311. H-W.Hennig, P.Neu and P.Sartori. 2. Naturforsch., Teil B. 41(1986)859. F.Mercier. S.Holand and F.Mathey, J. Organomet. Chem., 316(1986)271. U.Baumeister, H.Hartung, K.Jurkschat and A.Tzschach, J. Organomet. Chem., 304(19861107. J.L.Bookham. W.McFarlane and I.J.Colquhoun, J. Chem. sot., Chem. Commun.. (198611041. M.Antberg. L.Dahlenburg, N.Hock and C.Prengel. Phosphorus Sulfur, 26(1986)143. M.L.J.Hackney and A.D.Norman, J. Chem. Sot., Chem. Commun.. (1986)850. S.Heitkamp, T.Lebbe. C.U.Spiegel and O.Stelzer, Z. Naturforsch.. Teil B. 42(1987)177. S.Hietkamp and O.Stelzer. Chem. Ber., 119(1986)2921. H.Schmidbaur and T.Pollok, Angew. Chem., Int. Ed. Engl., 25(19861348. F.Cecconi. C.A.Chilardi. S.Midollini and A.Orlandini, Inorg. Chem.. 25(1986)1766.

145

225 226 227 228

229

230 231 232 233 234 235 236 237 238 239

240 241 242 243 244 245 246 247 248 249 250

J.Suara, E.Fluck, J.J.Stezowski and A.Maier, 2. Anorg. Allg. Chem., 545(1987)47. F.A.Cotton and P.A.Kibala. J. Am. Chem. Sot., 109(1987)3308. L.V.Tsymbal. E.I.Sinyavskaya, K.B.Yatsimirskii and V.C.Yurchenko, Russ. J. Inorg. Chem.. 32(1987)680. P.F.Barron. J.C.Dyaso.n, P.C.Healy, L.M.Engelhardt. B.W.Skelton and A.H.White, J. Chem. Sot., Dalton Trans., (198611965. D.J.Brauer, P.C.Knuppel and O.Stelzer, Chem. Ber., 120(1987)81. H.H.Karsch, A.Appelt and C.Muller, Angew. Chem., Int. Ed. Engl., 25(1986)823. A.L.Balch. L.A.Fossett. R.R.Cuimerans, M.M.Olmstead and P.E.Reedy Jr., Inorg. Chem., 25(198611397. E.Lindner. H.A.Mayer and P.Wegner. Chem. Ber., 119(1986)2616. C.U.Spiegel and O.Stelzer, 2. Naturforsch, Teil B, 42(1987)579. M.M.Taqui Khan and V.V.S.Reddy, Inorg. Chem., 25(1986)208. W.Schirmer, U.Florke and H-J.Haupt. 2. Anorg. Allg. Chem., 545(1987)83. M.Atoh, K.Kashiwabara and J.Fujita. Bull. Chem. Sot. Jpn., 59(1986)1001. A.M.Arif. J.C.Hefner, R.A.Jones and B.R.Whittlesey, Inorg. Chem.. 25(1986)1080. J.Grobe and N.Krummen. Z. Naturforsch.. Teil B. 41(198611239. D.J.Brauer, F.Col, S.Hietkamp, H.Peters, H.Sommer, O.Stelzer and W.S.Sheldrick, Chem. Ber., 119(1986)349. I.D.Williams and S.J.Lippard, L.Wei, A.Bell, S.Warner, J. Am. Chem. Sot., 108(1986)8302. S.J.McLain, Inorg. Chem.. 25(198613124. D.A.Dixon and B.E.Smart. J. Am. Chem. Sot., 108(1986)7172. W.W.Schoeller and J.Niemann, J. Am. Chem. Sot., 108(1986)22. H.Cerma and J.Navech. Phosphorus Sulfur, 26(19861327. A.Baceiredo and C.Bertrand, Phosphorus Sulfur, 26(1986)57. K-H.Dunker and F.Knoch, Chem. R.Appel, E.Caitzsch. Ber.. 119(1986)535. F.Knoch and C.Lenz, Chem. Ber., R.Appel. T.Caitzsch, 119(1986)1977. B.Neumuller and E.Fluck. Z. Naturforsch., C.Heckmann, Teil B, 42(1987)260. H.Schmidbaur, R.Pichl and C.Muller, Chem. Ber., 120(19871789. R.Pichl and C.Muller. Chem. Ber., H.Schmidbaur. 120(1987)39.

146

251 252 253 254 255 256 257 258 259

260 261 262 263 264 265 266 267

268

269

270 271 272 273 274 275 276 277

H.H.Murray and J.P.Fackler Jr., Acta L.C.Porter. Crystallogr., C43(1987)877. G.Muller, C.Kruger, C. Zybill and H.Schmidbaur. Acta Crystallogr., C42(1986)1141. J.M.Ball and P.M.Boorman, Acta J.F.Richardson, C42(198611271. Crystallogr., M.M.Turnball, E.H.Wong, E.J.Cabe and F.L.Lee, Inorg. Chem., 25(198613189. I.J.Colquhoun and W.McFarlane, S.O.Crim. S.A.Sangokaya, Inorg. Chem.. 25(1986)2699. Acta Crystallogr., N.Hmimid, J.P.Besse and R.Chevalier, C43(1987)782. G.Fritz and R.Biastock. Z. Anorg. Allg. Chem.. 535(1986163. C.Fritz and R.Biastock, W.Honle and H.C. von Schnering, 2. Anorg. Allg. Chem.. 535(1986)86. C.Fritz and R.Biastock. Z. Anorg. Allg. Chem.. 535(1986195. G.Fritz and P.Amann. Z. Anorg. Allg. Chem., 535(19861106. G.Fritz and D.Hanke, Z. Anorg. Allg. Chem., 537(1986)17. C.Fritz and K.Stoll. Z. Anorg. Allg. Chem.. 538(1986)78. G.Fritz and K.Stoll. Z. Anorg. Allg. Chem., 538(1986)113. C.Lindner and C.Scheytt, Z. Naturforsch., Teil B. 41(1986)10. M.Haase and U.Klingebiel, Z. Naturforsch.. Teil B, 41(1986)697. Phosphorus Sulfur, U.Starke, L.Rosch and R.Schmutzler, 27(19861297. M.Andrianarison. C.Couret, J-P.Declercq. A.Dubourg, J.Escudie and J.Satge, J. Chem. Sot., Chem. Commun.. (19871921. R.Ahlrichs, R.Becherer. M.Binneweis, H.Borrmann, S.Schunck and H.Schnockel, J. Am. Chem. M.Lakenbruk. sot., 108(1986)7905. R.Cereke and R.Schmutzler. M.Binnewies, H.Schnockel. Z. Anorg. Allg. Chem.. 534(1986)143. H.Schnockel and S.Schunck. 2. Anorg. Allg. Chem.. 548(1987)161. III and T.Kukunaga, J. Am. Chem. A.Dixon, A.J.Arduengo sot.. 108(198612461. A.J.Arduengo III, D.A.Dixon and D.C.Roe, J. Am. Chem. sot., 108(198616821. D.A.Dixon and A.J.Aeduengo III, J. Chem. Sot., Chem. Commun., (19871498. and D.Schomburg, L.Heuer, M.Sell, R.Schmutzler Polyhedron, 6(198711295. C.A.Bell and D.W.H.Rankin, J.Chem. Sot., Dalton Trans., (198611689. M.Meyer and U.Klingebiel, Z. Anorg. Allg. O.Graalmann, Chem.. 534(19861109. E.Fluck and B.Neumuller, Z. Anorg. Allg. Chem., 534(1986)27.

147

278 279

280 281 282 283 284 285 286 287 280

290

291 292 293 294 295 296 297 298 299

300 301 302 303 304 305

306 307 308

W.Honeise, W.Schwarz, C.Heckmann and A.Schmidt, Z. Anorg. Allg. Chem.. 533(1986)55. A.Schmidpeter and S.Lochschmidt, Angew. Chem.. Int. Ed. Engl., 25(19861253. E.Fluck. J.Suara. B.Neumuller. H.Riffel and H.Thurn. Z. Anorg. Allg. Chem.. 536(19861129. H.J.Frohn and H.Maurer. J. Fluorine Chem., 34(1986173. N.Weferling. Z. Anorg. Allg. Chem.. 548(1987)55. R.Ali and K.B.Dillon, Polyhedron. 5(198611197. W.Wolfsberger. J. Organomet. Chem., 317(19861167. R.M.Kren and H.H.Sisier, Inorg. Chim. Acta, lll(1986131. R.Ahlrichs. C.Ehrhardt. M.Lakenbrink. S.Schunck and H.Schnockel. J. Am. Chem. Sot., 108(1986)3596. D.Mootz and M.Wiebcke. Z. Anorg. Allg. Chem., 545(1987)39. C.Macho, R.Minkwitz, J.Rohmmann, B.Steger, V.Wolfel and H.Oberhammer. Inorg. Chem.. 25(198612828. R.Bartsch, J-V.Weiss and R.Schmutzler, Z. Anorg. Allg. Chem., 537(1986)53. 5(198611537. A.Finch. P.N.Gates and A.S.Muir. Polyhedron, J.Shamir, S.Schneider, A.Bino and S.Cohen, Inorg. Chim. Acta, 111(1986)141. A.Bino and S.Cohen, Inorg. Chim. J.Shamir, S.Schneider, Acta, 114(1986)35. L.Riesel and M.Kant, Z. Anorg. Allg. Chem., 530(1985)207. J.Cloede and R.Waschke, Phosphorus Sulfur, 27(19861341. J.Cloede, Z. Anorg. Allg. Chem.. 531(1985)17. J.Cloede and R.Waschke, Z. Anorg. Allg. Chem., 545(1987)184. P.Peringer and P-P.Winkler, Inorg. Chim. Acta, 118(1986lLl. W.Jansen and R.Ulses. Z. Anorg. Allg. Chem., 532(1986)197. R. de Jaeger and J.Heubel, Z. Anorg. Allg. A.Ouassini, Chem., 531(1985)188. R.M.K.Deng and K.B.Dillon, J. Chem. Sot., Dalton Trans., (198611843. R.M.K.Deng and K.B.Dillon, J. Chem. Sot.. Dalton Trans.. (198611443. P.B.Hitchcock, M.F.Lappert, A.K.Rai and H.D.Williams, J. Chem. Sot., Chem. Commun.. (198611633. F.Zurmuhlein and M.Regitz. Angew. Chem., Int. Ed. Engl., 26(1987183. J.Boske, E.Oando-Mavarez, E.Niecke, J.P.Majoral and J. Am. Chem. Sot., 109(1987)2822. G.Bertrand, U.Dressler, E.Niecke. S.Pohl, W.Saak, W.W.Schoeller and H.C. von Schnering. J. Chem. Sot., Chem. Commun., (198611086. W.S.Sheldrick and A.Schmidpeter, Chem. K.Karaghiosoff, Ber., 119(1986)3213. E.Franke and J.Kaub, Angew. Chem., Int. Ed. O.J.Scherer, Engl., 25(1986)96. K.Gobel and J.Kaub, Angew. Chem.. 1,nt. Engl., O.J.Scherer, 26(1987159.

148

309

310 311 312 313 314 315 316 317 318 319 320 321 322 323 324 325 326 327 328

329

330 331 332 333 334 335 336 337

A.H.Cowley, R.A.Kemp, J.C.Lasch, N.C.Norman, C.A.Stewart. B.R.Whittlesey and T.C.Wright, Inorg. Chem. 25(19861740. A.M.Arif and A.H.Cowley, J. Am. S.A.Weissman, S.C.Baxter, Chem. Sot., 108(1986)529. L.Riesel and D.Sturm, Z. Anorg. Allg. Chem.. 539(19861183. L.Riesel and D.Sturm. Z. Anorg. Allg. Chem., 539(1986)187. R.C.Haltiwanger. T.C.Hill and J.M.Barendt. H-J.Chen, Phosphorus Sulfur, 26(1986)155. A.D.Norman, R.C.Haltiwanger and A.D.Norman, M.L.Thompson, A.Tarassoli, Inorg. Chem.. 26(1987)684. S.S.Krishnamurthy. B.R.Vincent and S.S.Kumaravel, Z. Naturforsch., Teil B, 41(198611067. T.S.Cameron, B.Kottwitz and W.Kuchen, Phosphorus Sulfur, K.Diemert. 26(19861307. F-J.Wu and E.M.Holt, J. Organomet. Chem.. R.B.King. 314(1986)C27. E.Fluck, J.Svara and H.Riffel. Z. Anorg. Allg. Chem., 548(1987)63. A.Tarassoli, V.S.Allured, R.C.Haltiwanger and H.J.Chen. J. Organomet. Chem., 306(1986)C19. A.D.Norman. B-L.Li and R.H.Neilson. Inorg. Chem., 25(1986)361. R.R.Ford and R.H.Neilson. Polyhedron, 5(1986)643. and O.Stelzer, Chem. Ber., D.J.Brauer, F.Gol. S.Hietkamp 119(1986)2767. W.Buhlmeyer and K.Culdner, M.Herberhold. W.Ehrenreich, Chem. Ber., 119(198611426. A.Baceirodo and E.O.Mavarez, J-P.Majoral, G.Bertrand, Phosphorus Sulfur, 27(1986175. J-P.Majoral and J.Boske. E.Niecke. E.Ocando-Mavarez, Inorg. Chem.. 25(1986)2695. C.Bertrand, M.B.Hursthouse. H.C.Parkes. L.S.Shaw, R.A.Shaw and Phosphorus Sulfur, 28(1986)221. D.A.Watkins, J.Prihoda and C.Ohms. Z. Chem.. 27(19871178. E.Herrmann. H.W.Roesky: K.V.Katti. U.Seseke. U.Scholz, R.Herbst, E.Egert and C.M.Sheldrick. Z. Naturforsch., Teil B. 41(1986)1509. J.Fawcett. R.D.W.Kemmitt and D.R.Russell, K.W.Chiu. J. Chem. Sot.. Dalton Trans., (1986)457. U.Engelhardt and B.Stromburg, Acta Crystallogr.. C47(19871170. U.Engelhardt and K.Giersdorf, Acta Crystallogr., C42(198611830. U.G.Wettermark and R.H.Neilson, Inorg. Chem., 26(1987)929. G.Suss-Fink. Chem. Ber.. 119(1986)2393. K.Dostal, J.Sikola, M.Meisel and H.Grunze, Z. Anorg. Allg. Chem., 543(1986)199. C.Donath, M.Meisel, K-H.Jost, K.K.Palkina, S.I.Maksimova and N.T.Cibiskova. Z. Naturforsch., Teil B. 41(1986)1201. L.Riesel. D.Sturm. A.Nagel. S.Taudien, A.Beuster and Z. Anorg. Allg. Chem., 542(19861157. A.Karwatzki, L.Riesel. D.Sturm. A.Zschunke and B.Thomas, Z. Anorg. Allg. Chem., 544(1987)225.

149

338 339 340 341 342

343 344 345 346 347 348 349 350 351 352

353 354 355 356 357 358 359

360 361 362

363

D.Schomburg. U.Wermuth and R.Schmutzler. Phosphorus Sulfur. 26(1986)193. D.Schomburg. U.Wermuth and R.Schmutzler, Z. Naturforsch., Teil B. 41(1986)207. C.Trinquier, J. Am. Chem. Sot.. 108(19861568. H.R.Allcock, J.L.Desorcie and G.H.Riding. Polyhedron, 6(19871119. A.A. van der Huizen, J.C. van de Crampel, J.W.Rusch. T.Wilting, F. van Bolhuis and A.Meetsma, J. Chem. Sot., Dalton Trans., (198611317. A.I.Bortun, V.N.Belyakov and A.P.Kvashenko, Russ. J. Inorg. Chem., 31(1986)1413. J.K.Fincham. M.B.Hursthouse. H.C.Parkes. L.S.Shaw and B42(1986)462. R.A.Shaw. Acta Crystallogr., H.A.Al-Madfa. M.B.Hursthouse, H.G.Parkes, L.S.Shaw and R.A.Shaw, Phosphorus Sulfur, 28(19861203. S.Lanoux and R.H.Mas. Phosphorus Sulfur, 26(1986)139. H.R.Allcock, M.L.Levin and P.E.Austin, Inorg. Chem., 25(1986)2281. M.E.Ignatov, B.V.Levin, Z.C.Rumyantseva and E.C.Il'in, Russ. J.Inorg. Chem.. 31(1986)373. K.C.K.Swamy and S.S.Krishnamurthy, Inorg. Chem., 25(1986)920. P.L.Buwalda and J.C. van de Crampel, J. Chem. Sot., Chem. Commun.. (198611793. H.Winter and J.C. van de Crampel, J. Chem. Sot.. Dalton Trans., (198611269. M.Cleria. G.Audisio, S.Daolio. E.Vecchi, P.Traldi and S.S.Krishnamurthy. J. Chem. Sot., Dalton Trans., (19861905. Z.Kilic and R.A.Shaw. J. Chem. Sot., S.B.Contractor, Dalton Trans.. (198712023. H.R.Allcock, K.D.Lavin, C.H.Riding, R.R.Whittle and S(198611626. M.Parvez. Organometallics. M.Parvez and H.R.Allcock, K.D.Lavin. C.H.Riding, J. Chem. Sot., Chem.-Commun., (1986)117. D.E.Brown and C.W.Allen. Inorn. Chem.. 26(19871934. H.Winter and J.C. van de Crampel. J. Chem. SOC.. Dalton Trans., (198611389. W.Hoeve, K.S.Dhathathreyan, J.C. van de Crampel and F. van Bolhuis, Phosphorus Sulfur, 26(1986)293. F.J.Viersen, E.Bosma. B. de Ruiter, K.S.Dathathreyan, J.C. van de Crampel and F. van Bolhuis, Phosphorus Sulfur, 26(19861285. R.T.Oakley. J. Chem. Sot.. Chem. Commun., (19861596. L.Ya.Medvedeva and E.N.Beresnev, Russ. J. I.A.Rozanov. Inorg. Chem.. 32(19871623. H.Roesky. K.V.Katti. U.Seseke, M.Witt, E.Egert, R.Herbst and C.M.Sheldrick. Angew. Chem.. Int. Ed. Engl.. 25(1986)477. H.W.Roesky. K.V.Katti, U.Seseke. H-G.Schmidt, E.Egert, R.Herbst and C.M.Sheldrick. J. Chem. Sot., Dalton Trans., (19871847.

150

364 365 366 367 368 369 370 371 372 373 374 375 376 377 378 379

380 381 382 383 384 385 386 387

388 389 390

391 392

U.Seseke and H.W.Roesky, Inorg. Chem., K.V.Katti, 26(19871814. H.W.Roesky and B.Mainz, 2. Anorg. Allg. Chem., 540(1986)212. C.Rajca and J.Weidlein, 2. Naturforsch.. H-D.Hausen, Teil B. 41(1986)839. W.Mogelin and A.Balszuweit, 2. Anorg. Allg. K.Issleib, Chem., 530(1985)16. L.Riesel and M.Kant, Z. Anorg. Allg. Chem., 531(1985)73. and H.Gross. Z. Anorg. Allg Chem., J.Cloede, B.Costisella 535(19861221. J.Cloede. Z. Chem., 26(1986)247. J.P.Fackler. A.M.Mazany. R.A.Komoroski and D.W.Chasar, W.J.Kroenke, J. Am. Chem. Sot., 108(1986)5956. C.King, D.M.Roundhill and F.R.Fronczek, Inorg. Chem., 25(1986)1290. C.King. R.A.Auerbach. F.R.Fronczek and D.M.Roundhill, J. Am. Chem. Sac.. 108(198615626. S.Arabi, C.Bertholet. J-P.Barry, N.J.Taylor and B.Chaudret. Polyhedron, 5(198611785. V.Riera and M.A:Ruiz. J. Chem. Sot.. Dalton Trans.. (198612617. L.E.Carpenter II, B. de Ruiter, D. van Aken, H.M.Buck and J. Am. Chem. Sot., 108(198614918. J.G.Verkade. J.Loub and V.Petricek, Acta Crystallogr., R.Chmelikova. C42(1986)1281. J.R. van Wazar and C.S.Ewig. J. Am. Chem. Sot., 108(198614354. E.Fluck and J.Svara. Z. Naturforsch.. Teil B. G.Heckmann, 41(1986163. T.Mahmood and J.M.Shreeve. Inorg. Chem., 25(198613128. T.Mahmood and J.M.Shreeve. Inorn. Chem.. 25(198613830. T.Mahmood and J.M.Shreeve. Inor:. Chem., 25(1986)4081. F.Weller and A-F.Shihada, J. Organomet. Chem.. 322(1987)185. S.Dondi, M.Nardelli, C.Pelizzi and C.Predieri, J. Organomet. Chem., 308(1986)195. N.Burford. D.Kennepohl, M.Cowie, R.C.Ball and R.C.Cavell Inorg. Chem., 27(1987)650. J-P.Dutasta, J. Chem. Res. (Sl. (1986)22. R.Bohlen. J.Heine, W.Kuhn, W.Offermann, J.Stelten, G-V.Roschenthaler and W.G.Bentrude, Phosphorus Sulfur, 27(1986)313. R.Bohlen, H.Hacklin, J.Heine. W.Offfermann and C-V.Roschenthaler. Phosphorus Sulfur, 27(19861321. C-V.Roschenthaler, U. von Allworden and R.Schmutzler, 5(198611387. Polyhedron, V.W.Pogatzki, H.W.Roesky, K.S.Dhathathreyan, A.Thiel, H.G.Schmidt. M.Dyrbusch, M.Noltemeyer and G.M.Sheldrick, Chem. Ber. 119(198612687. W.M.Abdou and M.R.Mahran, Phosphorus Sulfur, 26(1986)119 R.Bohlen, R.Francke, J.Heine. R.Schmutzler and C-V.Roschenthaler. Z. Anorg. Allg. Chem., 533(1986)18.

151

393 394 395

396

397 398

399

400 401 402 403 404 405 406 407 408 409 410 411 412 413

414 415 416 417 418

H.W.Roesky. T.Cries, K.S.Dhathathreyan and H.Leuken, 2. Anorg. Allg. Chem.. 547(1987)199. B.V.L.Potter, J. Chem. Sot., Chem. Commun.. (1986121. V.I.Pakhomov. K.K.Palkina, S.I.Maksimova, N.T.Chibiskova, V.S.Mironova and I.V.Tananaev. Russ. J. Inorg. Chem., 32(1987)20. J.I.G.Cadogan. A.H.Cowley. I.Gosney, M.Pakulski, P.M.Wright and S.Yaslak. J. Chem. Sot.. Chem. Commun., (198611685. J.R.P.Arnold and C.Lowe. J. Chem. Sot., Chem. Commun., (1986)865. L.Criffiths, A.Root. R.K.Harris, K.J.Packer, A.M.Chippendale and F.R.Tromans, J. Chem. Sot., Dalton Trans., (1986)2247. C.M.Dobson and R.J.B.Jakeman, A.K.Cheetham. N.J.Clayden, J. Chem. Sot.. Chem. Commun., (19861195. E.H.Nordlander and J.H.Burns, Inorg. Chim. Acta, 115(1986)31. Acta Crystallogr.. B43(1987)23. M.Ichikawa. N.Ohama, M.Machida. T.Nakamura and Y.Kunifuji, Acta Crystallogr., C43(1987)962. Acta Crystallogr., C43(1987)367. P.G.Jones. C.Ferraris, H.Fuess and W.Joswig, Acta Crystallogr.. B42(1986)253. R.Kniep, Angew. Chem., Int. Ed. Engl., 25(1986)525. and C.Heymer, J.Arlt, M.Jansen, H.Klassen, C.Schimmel 2. Anorg. Allg. Chem.. 547(1987)179. D.Tran Oui and S.Hamdoune. Acta Crystallogr.. C43(1987)397. D.Eimerl and S.P.Velsko, A.Zalkin. D.H.Templeton, Acta Crystallogr., C42(1986)1686. B.I.Lazoryak, V.N.Colubev. N.L.Kishkin, A.A.Shvyryaev and R.C.Aziev, Russ. J. Inorg. Chem., 32(1987)753. M.J.Cresser. A.S.Tracey and K.M.Parkinson, J. Am. Chem. sot., 108(1986)6229. A.C.Nord and H.Annersten, Acta Chem. Stand., Ser. A, 41(1987156. A.Riou, Y.Cudennec and Y.Cerault, Acta Crystallogr., C43(1987)821. W.P.Bosman, P.T.Beurskens, J.M.M.Smits, H.Behm, J.Mintjens, W.Meisel and J.C.Fuggle. Acta Crystallogr., C42(1986)525. S.R.Wilson and J.R.Shapley, R.L.Keiter. D.S.Strickland, J. Am. Chem. Sot., 108(1986)3846. C.Arnau. M.Ferrer, M.Hartinez and A.Sanchez, J. Chem. sot.. Dalton Trans., (19861839. F.R.Fronczek and D.M.Roundhill, Inorg. R.El-Mehdawi. Chem., 25(1986)1155. F.R.Froncaek and D.M.Roundhill, Inorg. R.El-Mehdawi, Chem.. 25(1986)3714. and Y.Cerault, Acta Crystallogr., A.Riou, Y.Cudennec C43(1987)194.

152

419 420 421 422 423 424

425 426 427 428 429

430 431 432 433 434 435 436 437 438 439 440 441 442 443 444 445 446 447

S.V.Yakubovskaya, R.Ya.Melmikova and V.P.Titov. Russ. J. Inorg. Chem., 31(1986)1980 N.A.Akulin, C.Alvarez, R.Llavona. J.R.Carcia. M.Suarez and Inorg. Chem.. 26(1987)1045. J.Rodrigues, C.Alvarez, R.Llavona, J.R.Carcia, M.Suarez and J. Chem. Sot.. Dalton Trans., (1987)2045. J.Rodriguez, T.Kijima and S.Ueno, J. Chem. Sot., Dalton Trans., (1986)61. N.J.Clayden, J. Chem. Sot., Dalton Trans., (1987)1877. C.Ferragina. M.A.Massucci. P.Patrono, A.La Cinestra and A.A.C.Tomlinson, J. Chem. Sot., Dalton Trans., (19861265. N.T.Chibiskowa, K.Schlesinger S.I.Maksimova. K.K.Palkina. and C.Ladwig, Z. Anorg. Allg. Chem.. 529(1985189. V.V.Kokhanovskii. Russ. J. Inorg. Chem.. 32(1987)853. V.A.Lyutsko and T.I.Prisedskaya, Russ. J. Inorg. Chem., 31(1986)1789. S.Hamdoune and Y.Le Page, Acta Crystallogr.. D.Tranqui, C43(19871201. M.T.Averbuch-Pouchot, Z. Anorg. Allg. Chem.. 545(1987)118. P.Lightfoot and A.K.Cheetham, Acta Crystallogr., C43(1987)4. T.N.Galkova and E.A.Prodan, Russ. J. Inorg. Chem., 32(1987)675. U.Haubenreisser. Z. Anorg. Allg. Chem.. 532(19861157. M.T.Averbuch-Pouchot and A.Durif, Acta Crystallogr.. C43(1987)390. M.S.Bekhiria. M.Ben Amara and M.Dabbabi, Acta Crystallogr.. C43119871609. A.Jouini and M.Dabbabi, Acta Crystallogr., C42(19861268. M.T.Averbuch-Pouchot and A.Durif. Acta-Crystallogr.. C42(19861932. M.T.Averbuch-Pouchot and A.Durif, Acta Crystallogr., C42(1986)930. F.Schulz and M.Jansen, Z. Anorg. Allg. Chem.. 543(1986)152. M.T.Averbuch-Pouchot and A.Durif, Acta Crystallogr., C43(1987)631. M.T.Averbuch-Pouchot and A.Durif, Acta Crystallogr., C42(1986)129. M.T.Averbuch-Pouchot and A.Durif, Acta Crystallogr., C42(1986)131. A.Durif and M.T.Averbuch-Pouchot, Acta Crystallogr., C42(1986)927. M.T.Averbuch-Pouchot. Z. Anorg. Allg. Chem., 529(1985)143. U.Schulke and R.Kayser, Z. Anorg. Allg. Chem., 531(19851167. N.El-Horr and M.Bagieu-Beucher, Acta Crystallogr., C42(1986)647. N.El-Horr and M.Bagieu, Acta Crystallogr., C43(1987)603. M.T.Averbuch-Pouchot and A.Durif, Acta Crystallogr., C42(1986)928.

153

448 449 450 451 452 453 454 455 456 457 458 459

460 461 462 463 464 465 466 467 468 469

470 471 472 473 474 475 476 477

E.V.Murashova. V.K.Trunov and Yu.A.Velikodnyi. Russ. J. Inorg. Chem., 31(198611660. R.Claum. R.Cruehn and M.Moller, 2. Anorg. Allg. Chem., 543f19861111. K.H.Lii, R.C.Haushalter and C.J.O'Connor, Angew. Chem., Int. Ed. Engl., 26(1987)549. D.R.Corbin. J.F.Whitney. W.C.Fultz, G.D.Stucky, M.M.Eddy and A.K.Cheetham. Inorg. Chem.. 25(198612279. J.J.Pluth and J.V.Smith. Acta Crystallogr.. C42(198611118. J.J.Pluth and J.V.Smith, Acta Crystallogr., C43f19871866. J.J.Pluth, J.V.Smith and J.M.Bennett, Acta Crystallogr., C42(19861283. M.R.Gelsthorpe and C.R.Theocharis, J.Chem. Sot., Chem. Commun., (19861781. J.B.Parise. Acta Crystallogr.. C42(19861144. Acta Crystallogr., C42(1986)670. J.B.Parise, M.Bhattacharjee and M.K.Chaudhuri, J. Chem. Sot., Dalton Trans., (19871477. A-R.Grimmer, K-H.Jost. D.Muller and J.Neels, J. Fluorine Chem.. 34(19871347. J.Durand, L.Cot, M.Berraho and M.Rafiq, Acta Crystallogr.. C43f19871611. F.Mowius, B.Ziemer. G.Reck, M.Meisel and H.Grunze, Z. Anorg. Allg. Chem., 547(1987175. S.B.Etcheverry and E.J.Baran, Z. Naturforsch., A.E.Lavat. Teil B, 41(19861987. J. Fluorine Chem.. P.Vast. A.Semmoud and G.Palavit. 34(19861229. I.A.Rozanov and L.Ya.Medvedeva, Russ. J. Inorg. Chem., 31(1986)1729. L.M.Sukova, O.I.Kondratov, Yu.L.Gaft and K.I.Petrov, Russ. J. Inorg. Chem., 31(19861655. W.Feldmann, Z. Chem., 27(19871100. W.Feldmann, Z. Chem., 27(19871182. R.Hussong, H.Heydt and H.Regitz, Z. Naturforsch., Teil B, 41(19861915. E.Lindner, K.Auch, G.A.Weiss. W.Hiller and R.Fawzi, Chem. Ber.. 119(198613076. L.D.Ouin and J.Szewczyk, J. Chem. Sot., Chem. Commun., (19861844. B.M.Gimarc and J.J.Ott. J. Am. Chem. Sot., 108(198614298. B.H.Christiou, R.J.Gillespie and J.F.Sawyer, Acta Crystallogr., C43(19871187. T.Weber and U.Wickel. Z. Anorg. Allg. Chem., R.Blachnik, 532(1986)90. S.Albrecht and A.John, Z. Anorg. Allg. Chem., E.Herrmann, 545(19871202. Phosphorus J.Navech, M.Revel, R.Kraemer and S.Mathieu, Sulfur, 26(1986183. H.W.Roesky, R.Ahlichs and S.Grode, Angew. Chem., Int. Ed. Engl.. 25f1986182. M.A.Sarukhanov. I.A.Popova, Yu.Ya.Kharitonov and L.V.Kovalenko, Russ. J. Inorg. Chem.. 31(198612292.

154

478 479

480 481 482 483 484 485 486 487 488 489 490

491 492 493 494

495 496 497 498 499 500 501

502 503 504 505 506

M.Noltemeyer and C.M.Sheldrick. H.W.Roesky, Teil B, 41(1986)803. Z. Naturforsch.. J.Neels, B.Ziemer and M.Meisel, Z. Anorg. Allg. Chem., 542(1986)123. M.Noltemeyer and C.M.Sheldrick, H.W.Roesky. N.Benmohamed. Teil B, 41(1986)938. Z. Naturforsch.. P.Bourdauducq and M.C.Demarcq, J. Chem. Sot.. Dalton Trans., (198711897. J.Neels, A-R.Crimmer, M.Meisel, C-U.Wolf and H.Jancke, 2. Anorg. Allg. Chem., 547(1987)83. N.Kuhn and H.Schumann, J. Organomet. Chem., 304(1986)181. J.Hahn and T.Nataniel, Z. Anorg. Allg. Chem., 543(198617. Allg. Chem., T.Nataniel. Z. Anorg. J.Hahn and 548(1987)180. and P.Paneth, J. Am. Chem. Sot., P.A.Frey. W.Reimschussel 108(1986)1720. C.Donath and M.Meisel. Z. Anorg. Allg. Chem.. 549(1987)46. C.Ohms and M.Meisel, Z. Anorg. J.Prihoda, C.Crossmann. Allg. Chem.. 549(1987)59. J.E.Drake and A.B.Sarkar, J. Organomet. Chem., R.K.Chadha. 323(1987)271. and F.Huber. Acta Crvstallogr., H.Preut. V-D.Nao C42(1987)809. " H.Preut, V-D.Ngo and F.Huber, Acta Crystallogr.. C43(1987)164. H.Weichmann. J.Mennier-Pit-et and M. van Meersche. J. Organomet. them., 309(1986)273. D.B.Sowerby and I.Haiduc, J. Chem. Sot., M.J.Begley, Dalton Trans., (19871145. L.Silaghi-Dumitrescu, I.Haiduc, M.J.Begley, C.Silvestru, M.Nunn and D.B.Sowerby, J. Chem. Sot., Dalton Trans.. (198611031. M.J.Begley. D.B.Sowerby. D.W.Wesolek, C.Silvestru and Chem.. 316(1986)281. I.Haiduc, J. Organomet. M.Moran and I.Cuadrado. J. Organomet. Chem., 311(1986)333. P.C.H.Mitchell and T.Colclough, M.C.B.Drew, W.A.Hopkins, J. Chem. Sot., Dalton Trans., (1986)351. S.Martinez-Carrera and S.Carcia-Blanco. J.Sans-Aparicio, Acta Crystallogr.. C42(1986)1121. H.Wunderlich. Acta Crystallogr., C43(1987124. Y.P.Singh and R.C.Mehrotra, Polyhedron, 5(19861967. P.G.Harrison and T.Kikabhai. J. Chem. Sot., Dalton Trans., (19871807. P.G.Harrison. M.J.Begley, T.Kikabhai and F.Killer, J. Chem. Sot., Dalton Trans., (19861929. M.C.B.Drew. M.Hasan, R.J.Hobson and D.A.Rice. J. Chem. sot.. Dalton Trans., (198611161. P.G.Harrison. M.J.Begley, T.Kikabhai and F.Killer, J. Chem. Sot., Dalton Trans., (19861925. A.J.Burn. P.Mechan and K.M.A.Parker. R.W.Joyner, J. Chem. Sot., Chem. Commun.. (19861982. H.Wunderlich. Acta Crystallogr.. C42(1986)631.

155

507 508 509 510 511 512 513 514 515 516 517 518 519 520 521 522 523 524 525 526 527 528 529

530 531 532 533 534 535

H.Wunderlich, Acta Crystallogr., 838(19821614 T.Imai. M.Shimoi and A.Ouchi, Bull. Chem. Sot. Jpn., 59(19861669. K.Nagai, Y.Ohki. Y.Suzuki, M.Shimoi T.Imai, M.Nakamura, and A.Ouchi. Bull.- Chem. Sot. Jpn., 59(198612115. M.Z.Jandall. C.Eulenberger and H.Hahn. Z. Anorg. Allg. Chem., 530(19851144. M.Fuchs. W.Kuchen and W.Peters. Chem. Ber.. 119(198611569. M.Fuchs. W.Kuchen and W.Peters, Z. Anorg. Allg. Chem., 545(1987175. J.Neels. K-H.Jost, M.Meisel, K.K.Palkina, S.I.Maksimova and N.T.Tshibiskova, Z. Anorg. Allg. Chem.. 540(19861307. J.R.Rollo and R.J.H.Clark, Inorg. Chem., C.R.Burns. 25(198611145. C.Schneider and U.Wickel, R.Blachnik. W.Buchmeier, Z. Naturforsch., Teil B., 42(1987147. S,Kubiniok and T.Severenges, Z. Anorg. Allg. W-W.duMont, Chem., 531(1985121. N.Kuhn, H.Schumann and C.Wilmershauser. Z. Naturforsch.. Teil B, 42(19871674. N.Kuhn and H.Schumann. Phosphorus Sulfur, 26(1986)199. V.K.Cupta, L.K.Krannich and C.L.Watkins, Inorg. Chem., 26(198711638. A.L.Rheingold and M.E.Fountain, Organometallics. 5(1986)2410. A.J.DiMaio and A.L.Rheingold, J. Chem. Sot., Chem., Commun., (19871404. H.Sitzmann and G.Wolmershauser, O.J.Scherer, J. Organomet. Chem., 309(1986177. A.L.Rheingold and A-J.DiMaio, Organometallics, 5(19861393. A.J.DiMaio and A.L.Rheingold, Angew. Chem., P.Mercando, Int. Ed. Engl.. 26(19871244. J.Ellermann. M.Moll and L.Brehn, Z. Anorg. Allg. Chem., 539(1986)50. R.H.Haushalter, J.Chem. Sot., Chem. Commun., (19871196. C.Belin and H.Mercier, J. Chem. Sot., Chem. Commun., (19871190. B.Eisenmann. H.Jordan and H.Schafer, Z. Anorg. Allg. Chem.. 530(1985174. H-G. von Schnering. J.Wolf, D.Weber, R.Ramirez and T.Meyer. Angew. Chem.. Int. Ed. Engl., 25119861353. G.Wenski and A.Mewis, Z. Anorg. Allg. Chem., 535(19861110. R.W.H.Small and I.J.Worrall, Inorg. Chim. A.Boardman, Acta. 121(1986)L35. A.T.McPhail and C.G.Pitt, R.L.Wells, A.P.Purdy. J. Organomet. Chem., 308(19861281. R.L.Wells, A.P.Purdy. K.T.Higa. A.T.McPhail and C.C.Pitt, J. Organomet. Chem., 325(19871C7. and R.L.Wells, Inorg. C.C.Pitt, K.T.Higa, A.T.McPhail Chem., 25(1986)2483. A.P.Purdy, K.T.Higa and R.L.Wel1.s. C.C.Pitt, Organometallics, 5(1986)1266.

156

536 537 538 539 540 541

542 543 544 545

546 547 548 549 650

551 552 553

554 555 556 557 558 559 560 561 562

A.T.McPhail and C.G.Pitts. J. Chem. R.L.Wells. A.P.Purdy. sot., Chem. Commun., (1986)487. C.Marki and H.Sejpka, Angew. Chem.. Int. Ed. Engl., 25(19861264. J.Grobe and D.Le Van, J. Organomet. Chem.. 311(1986)37. L.Weber. G.Meine and R.Boese, Angew. Chem.. Int. Ed. Engl., 25(1986)469. J.M.Chehayber and J.E.Drake, Inorg. Chim. Acta, 112(1986)209. J.Ellermann, L.Brehm. E.Lindner. W.Hiller, R.Fawzi, F.L.Dickert and M.Waidhas, J. Chem. Sot., Dalton Trans., (19861997. A.Veit and M.Moll, J. Organomet. Chem., J.Ellermann, 299(1986)51. C.Becker, B.Becker. M.Birkhahn. O.Mundt and R.E.Schmidt, Z. Anorg. Allg. Chem.. 529(1985)97. M.F.Lappert and S.J.Smith, J. Organomet. P.B.Hitchcock. Chem., 320(1987)C27. R.A.Bartlett, H.V.R.Dias. H.Hope, B.D.Murray. M.M.Olmstead and P.P.Power, J. Am. Chem. Sot., 108(1986)6921. A.M.Arif, R.A.Jones and K.B.Kidd. J. Chem. Sot., Chem. Commun.. (1986)1440. R.A.Jones and B.R.Whittlesey. Inorg. Chem.. 25(1986)852. A.C.Filippou. E.O.Fischer. K.Ofele and H.C.Alt, J. Organomet. Chem., 308(1986)11. D.Fenske and J.Hachgenei, Angew. Chem., Int. Ed. Engl.. 25(1986)175. C.Elschenbroich, J.Kroker, W.Masa, M.Wunsch and A.J.Ashe III, Angew. Chem.. Int. Ed. Engl., 25(1986)571. A.J.Ashe III, S.Mahmoud. C.Elschenbroich and M.Wunsch, Angew. Chem.. Int. Ed. Engl.. 26(19871229. P.Raj. K.Singhal and R.Rastogi. Polyhedron, 5(19861677. C.A.McAuliffe, B.Beagley. C.A.Cott. A.C.Mackie, P.P.MacRory and R.G.Pritchard, Angew. Chem., Int. Ed. Engl.. 26(1987)264. R.E.Humphries. N.A.A.Al-Jabor. D.Bowen, A.G.Massey and C.B.Deacon. J. Organomet. Chem.. 319(1987)59. H.Preut. R.Kasemann and D.Naumann, Acta Crystallogr., C42(1986)1875. Y.Shen. Z.Fan and W.Qiu, J. Organomet. Chem.. 320(198712 1. J.Wolf, D.Weber and H.G. von Schnering, Z. Naturforsch., Teil B, 41(19861731. H.Schmidbaur. W.Bublak. B.Huber and C.Muller, Angew. Chem.. Int. Ed. Engl., 26(19871234. H.J.Frohn and H.Maurer, J. Fluorine Chem., 34(1986)129. W.Willing, U.Muller, J.Eicher and K.Dehnicke, Z. Anorg. Allg. Chem.. 537(1986)145. D.Mootz and M.Wiebcke, Inorg. Chem., 25(198613095. D.Cantar. B.Frlec. D.R.Russell and J.H.Holloway, Acta Crystallogr.. C43(1987)618.

157

563 564 565 566 567 568 569 570 571 572 573 574 575 576 577 578 579 580 581 582 583 584 585 586 587 588 589 590 591

A.Apblett. T.Chivers and J.F.Richardson, Can. J. Chem., 64(19861849. and L.Carlsen. J. Chem. S.Elbel, C.Runger, H.Egsgaard Res. (Sl, (19861294. R.Minkwitz and H.Prenzel, 2. Anorg. Allg. Chem., 534(1986)150. R.Minkwitz and H.Prenzel. Z. Anorg. Allg. Chem., 548(19871103. V.K.Cupta, L.K.Krannich and C.L.Watkins, Inorg. Chem.. 25(198612553. V.K.Cupta, L.K.Krannich and C.L.Watkins, Inorg. Chim. Acta, 126(1987)173. V.K.Cupta, L.K.Krannich and C.L.Watkins, Polyhedron, 6(198711229. L.K.Krannich and C.L.Watkins, J. Chem. Sot., R.K.Kanjolia. Dalton Trans., (198612345. R.K.Kanjolia and C.L.Watkins. Inorg. Chim. L.K.Krannich, Acta, 114(1986)159. M.Herberhold. K.Guldner. A.Cieren. C.Ruiz-Perez and T.Hubner, Angew. Chem., Int. Ed. Engl., 26(1987182. M.Herberhold and K.Culdner. Z. Naturforsch., Teil 8.. 42(1987)118. A.H.Cowley and M.Pakulski. J. Chem. Sot., Chem. A.M.Arif, Commun., (19871165. J.Ellermann and A.Veit, Chem. Ber.. 119(19861766. W.S.Sheldrick and H-J.Hausler. Z. Anorg. Allg. Chem., 538(1986145. W.S.Sheldrick and H-J.Hausler, Z. Anorg. Allg. Chem., 549(19871177. A.K.Brisdon. R.A.Comme and J.S.Ogden, J. Chem. Sot., Dalton Trans., (198612725. R.H. de Almeida Santos and J.R.Lechat. C.Lariucci, Acta Crystallogr.. C42(19861731. B.A.Borgias, G.C.Hardin and K.N.Raymond, Inorg. Chem., 25(198611057. Yu.M.Kuznetsov,'N.A.Mazhenov, A.Z.Beilina B.K.Kasenov, and C.B.Saduova, Russ. J. Inorg. Chem., 32(19871102. N.C.Chernorukov and C.F.Sibrina. Russ. J. Inorg. Chem., 32(1987)615. E.Fanchon. J.Vicat, D.Tran Qui and A.Boudjada, Acta Crystallogr.. C43(198711022. C.D.Nigam and G.Mattern, R.N.P.Choudhary, T.V.Narasaiah, Acta Crvstallonr.. C43(19871388. Act: Crystallogr., C42(19861774. F.Pertlik, F.Pertlik, Acta Crystallogr.. C43(19871381. H.Effenberger, Acta Crystallogr., C43(19871399. D.Tran Oui and M.Chiadmi, Acta Crystallogr., C42(1986 1391. P.Keller and H.Hess, Z. Anorg. Allg. Chem., H.Riffel, 530(1985160. R.Enjalbert, P.Lecante and J.Caly, Acta Crystallogr., C42(198611465. P.P.Mahapatra, L.M.Mahapatra and B.Mishra, Polyhedron 6(198711049.

158

592 593 594 595 596 597 598 599

600 601 602 603 604 605 606 607 608 609

610 611 612 613 614 615 616 617 618

A.V.Steblevskii. A.S.Alikhanyan, A.S.Pashinkin and V.I.Gorgoraki. Russ. J. Inorg. Chem., 31(1986)945. A.V.Steblevskii. A.S.Alikhanyan, A.S.Pashinkin and V.A. Malyusov, Russ. J. Inorg. Chem.. 31(198611415. H.Brunner, H.Kauermann. B.Nuber, J.Wachter and M.L.Ziegler, Angew. Chem., Int. Ed. Engl., 25(19861557. U.Muller and A.T.Mohammed, Z. Anorg. Allg. Chem., 533(1986)65. E.W.Abel, M.A.Beckett. P.A.Bates and M.B.Hursthouse, J. Organomet. Chem., 325(1987)261. E.W.Abel and M.A.Beckett, Polyhedron, 6(198711255. M.Di Vaira, M.Peruzzini and P.Stoppioni, Polyhedron, 5(1986)945. W.S.Sheldrick and J.Kaub, Z. Anorg. Allg. Chem.. 535(1986)179. J.Kaub, Z. Naturforsch.. Teil B, 41(1986)436. A.P.Curshumov. M.I.Murguzov, Z.Z.Nadzhafova, A.M.Akhmedov and S.Sh.Eivazov, Russ. J. Inorg. Chem., 31(19861150. A.P.Gurshumov, M.I.Murguzov, Z.Z.Nadzhafova, A.M.Akhmedov and S.Sh.Eivazov, Russ. J. Inorg. Chem., 31(1986)151. M.R.Allazov, Sh.M.Shirinov and A.A.Movsum-Zade, Russ. J. Inorg. Chem., 31(1986)257. H.J.Breunig and S.Gulec, Z. Naturfosch.. Teil B, 41(1986)1387. H.J.Breunig and D.Muller. Z. Naturforsch., Teil B, 41(1986)1129. H.J.Breunig, A.Soltani-Neshan. K.Haberle and M.Drager, Z. Naturforsch., Teil B, 41(1986)327. C.Cordier. H.Schafer and M.Stelter. Z. Anorg. Allg. Chem., 534(1986)137. L.D.Freedman and C.O.Doak. J. Organomet. Chem., 298(1986137 L.D.Freedman and G.O.Doak, J. Organomet. Chem.. 324(1987)1. M.Ates, H.J.Breunig, A.Soltani-Neshan and M.Tegeler, Z. Naturforsch.. Teil 8. 41(19861321. H.Preut. U.Praeckel and F.Huber, Acta Crystallogr.. C42(1986)1138. H.F.Martens and H.A.Meinema, J.C.Stevens, J.M.Trooster. Inorg. Chim. Acta, 115(19861197. R.R.Holmes. R.O.Day, V.Chandrasekhar and J.M.Ho1me.s. Inorg. Chem.. 26(1987)157. R.R.Ho1me.s. R.O.Day, V.Chandrasekhar and J.M.Holmes, Inorg. Chem.. 26(1987)163. H.Preut. M.Domagal and F.Huber, Acta Crystallogr.. C43(1987)416. V.K.Jain, J.Mason and R.C.Mehrotra, J. Organomet. Chem., 309(1986)45. C.Ferguson, C.Clidewell, B.Kaitner. D.Lloyd and S.Metcalfe, Acta Crystaliogr.. C43(19871824. R.Ruther. F.Huber abd H.Preut, Z. Anorg. Allg. Chem., 539(1986)110.

159

619 620 621 622 623 624 625 626 627 628 629 630 631 632 633 634 635 636 637 638 639 640 641 642 643 644

H.Preut, R.Ruther and F.Huber, Acta Crystallogr., C42(1986)1154. R.Normura, M.Yamamoto. A.Takabe and H.Matsuda, Polyhedron, 6(198711161. F.Huber. T.Westhoff and H.Preut, J. Organomet. Chem., 323(1987)173. K.Akiba, H.Fujikawa, Y.Sunaguchi and Y.Yamamoto, J. Am. Chem. Sot.. 109(1987)1245. V.I.Kostin and L.N.Ignateva, J. Fluorine V.I.Sergienko, Chem., 32(1986)367. W.A.S.Nandana, J.Passmore, P.S.White and C.M.Wong, J. Chem. Sot., Dalton Trans., (198711989. T.M.Shchegoleva, L.D.Iskhakova, A.A.Shakhnazaryan and V.K.Trunov. Russ. J. Inorg. Chem., 31(1,986)515. D.Mootz and V.Handler, 7.. Anorg. Allg. Chem.. 533(1986123. C.R.Willey and C.B.Drew, J. Chem. Sot., P.P.K.Claire, Dalton Trans., (19871263. E.A.Kravcenko. M.J.Burtzev and M.Meisel. Z. Anorg. Allg. Chem.. 547(1987)173. A.L.Rheingold. S.J.Ceib, M.Shieh and K.H.Whitmire, Inorg. Chem., 26(1987)463. A.H.Cowley and M.Pakulski, J. Chem. Sot., A.M.Arif, Chem. Commun., (19871622. A.H.Cowley, N.C.Norman and M.Pakulski, A.M.Arif, Inorg. Chem.. 25(198614836. and D.B.Sowerby, J. Chem. M.Hall. M.Nunn, M.J.Begley sot., Dalton Trans., (198611231. J. Chem. Sot., M.Hall, M.Nunn and D.B.Sowerby. Dalton Trans., (198611239. J. Chem. M.J.Begley, M.Hall. M.Nunn and D.B.Sowerby. sot., Dalton Trans., (198611735. H.Preut, F.Huber and C.Alonzo, Acta Crystallogr., C43(1987)46. Angew. Chem., S.Pohl, W.Saak, P.Mayer and A.Schmidpeter, Int. Ed. Engl., 25(19861825. S.Pohl, W.Saak and D.Haase, Angew. Chem., Int. Ed. Engl., 26(19871467. O.Scheidsteger, H.Berke and C.Huttner, J. Organomet. Chem., 311(1986)85. G.Rajca and J.Weidlein, Z. H-D.Hausen, W.Schwarz, Teil 8, 41(198611223. Naturforsch., J-E.Kessler. C.T.G.Knight and A.E.Merbach, Inorg. Chim. Acta, 115(1986)75. C.T.C.Knight and A.E.Merbach. Inorg. Chim. J-E.Kessler, Acta, 115(1986185. H.Preiss. U.Nissel and H.Sprenger, Z. Anorg. Allg. Chem., 543(19861133. M.Coerlich and H.Sprenger, Z. Anorg. Allg. H.Preiss, Chem., 533(1986)37. A.Lehmann and H.Sprenger, Z. Anorg. Allg. Chem., H.Preiss, 543(19861143.

160

645 646 647 648 649

650 651 652 653 654 655 656 657 658 659 660 661 662 663 664 665 666 667 668 669 670 671 672

and A.Schmidt, Z. Anorg. Allg. Chem., S.Blosl, W.Rozdzinski 538(1986161. S.Brownstein, E.Gabe, F.Lee and A.Piotrowski, Can. J. Chem., 64(1986)1661. U.Ensinger, W.Schwarz, B.Schrutz, K.Sommer and A.Schmidt, Z. Anorg. Allg. Chem., 544(1987)181. L.G.Pedersen and M.M.Bursey, Inorg. Chim. J.P.Kiplinger, Acta, 115(1986)203. M.Gajhede and S.Larsen. Acta Crystallogr., B42(19861172. C.Cascales and I.Rasines. J. Chem. Sot., Dalton Trans., (198611247. T.Birchall. C.Hallett and A.W.Sleight, J. Chem. Sot., Dalton Trans., (1986)853. G.Tatzel, N.Creune, J.Weidlein and E.Jacob. Z. Anorg. Allg. Chem., 533(1986)83. 6(1987)411. R.Nomura, A.Takabe and H.Matsuda, Polyhedron, H.M.Hoffmann and M.Drager, Z. Naturforsch., Teil 8. 41(1986)1455. M.Hall. D.B.Sowerby and C.P.Falshaw, J. Organomet. Chem., 315(1986)321. H.M.Hoffmann and M.Drager. J. Organomet. Chem., 320(1987)273. P.Raj. R.Rastogi. K.Singhal and A.K.Saxema, Polyhedron, 5(1986)1581. W.S.Sheldrick and J.Kaub, Z. Anorg. Allg. Chem.. 536(1986)114. M.Wieber and I.Sauer. Z. Naturforsch., Teil B, 42(1987)695. W.L.Wilson, R.W.Rudolph, L.L.Lohr, R.C.Taylor and P.Pyykko. Inorg. Chem., 25(198611535. J.M.Wallis, G.Muller and H.Schmidbaur, J. Organomet. Chem.. 325(19871159. J.M.Wallis, G.Muller and H.Schmidbaur, Inorg. Chem., 26(1987)458. K.H.Whitmire, K.S.Raghuveer. M.R.Churchill, J.C.Fettinger and R.F.See, J. Am. Chem. Sot., 108(198612778. G.O.Doak and L.D.Freeman, J. Organomet. Chem., 298(1986)67. G.O.Doak and L.D.Freedman, J. Organomet. them., 324(1986)39. G.B.Deacon, P.W.Felder, M.Domagala. F.Huber and R.Ruther, Inorg. Chim. Acta. 113(1986)43. A.Schier, J.M.Wallis. G.Muller and H.Schmidbaur. Angew. Chem.. Int. Ed. Engl., 25(1986)757. W.Frank, J.Weber and E.Fuchs, Angew. Chem., Int. Ed. Engl.. 26(1987)74. F.Lazarini. Acta Crystallogr.. C43(19871637. L.P.Battlaglia. A.B.Corradi, R.Battistuzzi and T.Manfredini, Inorg. Chim. Acta. 121(1986)131. F.Lazarini, Acta Crystallogr., C43(19871875. K.B.Dzeranova. C.A.Bukhalova, N.I.Kaloev and I.V.Mardirosova, Russ. J. Inorg. Chem.. 31(1986)160.

161

673 674 675 676

677 678 679 680 681 682 683

K.B.Dzeranova. G.A.Bukhalova, N.I.Kaloev and I.V.Cazdanov. Russ. J. Inorg. Chem.. 31(198611326. V.A.Trifonov and B.A.Popovkin, Russ. J. E.V.Dikarev, Inorg. Chem., 32(19871430. J.Ketterer and V.Kramer. Acta Crystallogr., C42(198611098. A.Yu.Shashkov, V.A.Efremov, A.A.Bush, N.V.Rannev, Yu.N.Venevtsev and V.K.Trunov, Russ. J. Inorg. Chem., 31(198611391. A.A.Bush and Yu.N.Venevtsev, Russ. J. Inorg. Chem.. 31(19861769. P.K.Bharadwaj and W.K.Husker, Inorg. Chem., 26(198711453. E.Casassas and T.Visa, Polyhedron, 5(1986)1513. A.Muller. M.Zimmermann and H.Bogge, Angew. Chem., Int. Ed. Engl., 25(19861273. P.Lemoine, D.Carre and M.Guittard. Acta Crystallogr., C42(19861259. C42(198611089. V.Kramer, Acta Crystallogr.. V.Kramer and I.Reis, Acta Crystallogr.. C42(19861249.