Elements of group 1

1

CoordiMtionChemistryReolews,lOZ (1990)1-110 Elsetier SciencePublishers B.V.,Amsterdam-Printed

inTheNetherlands

Chapter 1 ELEMENTS OF GROUP 1 Peter Hubberstey 1.1

INTRODUCTION ..........................................

2

1.2

THE ELEMENTS ..........................................

3

1.3

SIMPLE COMPOUNDS OF THE ALKALI METALS .................

4

Ion Pairs ........................................ Theoretical Treatment of Small Moieties .......... Intermetallic Compounds .......................... Binary Compounds ................................. Ternary germanides and pnictides ................. Ternary oxides and chalcogenides ................. Ternary halides .................................. Intercalates .....................................

4 6 12 14 20 22 27 31

COMPOUNDS OF THE ALKALI METALS CONTAINING ORGANIC MOLECULES OR COMPLEX IONS .... ... .... .. .. ... .. .. .. .. .. .

33

1.3.1 1.3.2 1.3.3 1.3.4 1.3.5 1.3.6 1.3.7 1.3.8 1.4

Complexes of Acyclic Lipophilic Ionophores ....... Crown complexes .................................. Complexes of Lariat Ethers ....................... Complexes of Macrocyclic Polyethers of Novel Design ........................................... Natural Product Ionophores ....................... Cryptates and Related Complexes .................. Salts of Carboxylic, Thiocarboxylic and Dithiocarbamic Acids ......................... Heterobimetallic Complexes containing Alkali Metals ........................................... Lithium Derivatives ..............................

z: 54

Hexamers and Higher Oligomers ................. Tetramers ..................................... Trimers ....................................... Dimers ........................................ Monomers and Polymers ......................... Solution Chemistry ............................

72 76 78 78 84 91

1.4.10

Sodium Derivatives ...............................

94

1.4.11

Potassium, Rubidium and Caesium Derivatives ......

95

REFERENCES

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

99

1.4.1 1.4.2 1.4.3 1.4.4 1.4.5 1.4.6 1.4.7 1.4.8 1.4.9

1.4.9.1 1.4.9.2 1.4.9.3 1.4.9.4 1.4.9.5 1.4.9.6

34 38 44

57 60 71

2

1.1

INTRODUCTION

Since earth

the

principal

metal

format

chemistry

adopted

literature Thus

the

topics

diverse

of

is

metals

considered

is

discussed

Alkalides

and

groups.[2-61 of

crystallised

et

[(18C61,Csl+ that

from

and

Cs’ are

not

provided

by

of

the

they

et

chemical

a1.[31

(4

= -60+2ppm

of for

[(15C51,Csl’), dependent and

6 =

-205

to

et

al.

in

Spectroscopic presence

of

-240ppm

studies

for

and

a

which at

has

remote neighbours

also

been

spectral Dye

for

et

the

data a1131

for have

alkalides

(M = Na-Fib). the

of

d = +27*3ppm

-50ppm

The

alkalide

for

which

to

sites

cationic

n.m.r.

data

eight

unremarkable.[21

anionic

one

black

spherical,

by

are

eight

as

nearly

independent

= -40

was

shows for

temperature

[(18C6l,Csl’

Cs-I. that

15C5[51

(optical, metal

in

on any

are

crystal

which

[(15C51,CsJ+H-

and

shown

reviewed

independent

first

surrounded

[(18C61zCsl’Cs(6

groups

only

not

mixtures

all

spectral

ions

shifts,

12C4[41

alkali

the

‘eJCs-mas

and

for

have

trapped

from

Cs+

the

The

three

= 0.0,0.2,0.8,1.01.

[(18C61zCsl’

chemical

Edwards dissolve

the

except

of

with

n.m.r.

two

is

is

by

trapped 240pm

localised

cll = Na-Csl

shifts

pursued

geometries are

(x

[(18c6l,csl+M-

is

interact

‘33Cs-mas

reported

it

metals,

decribed

radius

preferentially

the

Chapter.

[(18C61,Csl’e-,

electron

[(18C6),Csl’e-1_,Na-, also

have

electrons

that

on

crowns,

of

of

repetition,

of

papers

considered

chemistry

groups

been

viz.,

the

of

complexes

this

in

significance

elsewhere.

have

of

reviews.

number

are

of

detail

a1.[21

The

Dye

avoid

both

in

cavity

cations,

Evidence

to

the

1987

discussed

dimethylether-trimethylamine

platelets. empty,

the

alkaline

years,

and

limited

notably

section

electride,

from

otherwise

that,

a

are

subjects

topics,

electrides

an

only

recent

earlier

importance

pertinent

Dye

structure

and

similar

the

and

papers

current

and

1986-June

of

complexants,

in

in

Jan.

1985[11

unconnected

chemistry

it

the

alkali

abstracted

certain

related

organometallic as

and

so

the

in

little

of

elements;

For

and

changed

of

the

individual

cryptates

shiny

those of

basis.

interests

review

covering

describing

here

have this

majority

than

latter

for

mirrors

sections rather

research

cations

the to

alkali

give

e.s.r. and

metals

intense and

anions,

n.m.r.1

(M = Na-Csl

blue

solutions. revealed

electrons

and

the

3 cation-electron 990+201. high

pairs.

field

“%s-

not observed.

spectroscopic

in hmpa-thf

mixtures

indicate three

Three

of

alkali

improves

addition syngas

attributable were

to

detected

in

merged to give

saturated

the only

describing

metal

cation

anionic

a single

aspects

of

promoters

dimerisation

and

the cocatalytic

of of

greatly

the formyl

present

ion.

doping

to methanol;[81

K’ stabilises

sodium et

in carbonatei

and selectivity

oxidative

of

by Saji

species Na-

have been published;

the

solutions

effected

a single

Cs” to CufZnO catalysts

with state

sodium

23Na-mas n.m. r.

salts,

solvates

The =%Na chemical

shifts

solution

and where

coupling

effects;

with

and H’

MCOs (M

(M = = Sr,Ba)

methane;171

increases

the

and doping

intermediates

whereas

interatomic

were

for

the

NaF or NaCl

only

of

were measured

and complexes

differing

spectra

and complexes

necessary

d *r 8ppm for

solvates

1.2

6 =

rate

of

of

Ru/Al,O,

formed

in

conversion.t91

Solid

ion,

of

solvate

{CO + Hz3 conversion

syngas

(from

is

the activity

for

of

catalysts

the

Na-

catalysts

as catalysts

of

that

hmpa molecules

oxide[8,9] Li-Rb)

studies

(O.O61
communications

function

resonances

at

due to =‘=K- and

signals pairs

Na-;

peaks

signal.

Optical al.161

the

n.m.r.

= 10 Hz for

Two e.s.r.

on melting

singlet

resonances

and cation-electron

solution:

time averaged

Rb-1

optical

Rb - 890-+20; Cs -

gave

ppm, CLu,,,

= 1000 H, for

electrons

had characteristic

K - 840220;

and -=Rb-

(6 = -61.820.1 hu,,,

were

solvated frozen

23Na-

Although

-191*2ppm,

that

The anions

f X,,, /nm: Na - 670*10;

bands

with

they

the

a comprehensive

relative

corrected salts

they

to

for

ligand

varied

with

NaCl

the anion

NaBPh4).

independent molecule

1M aqueous

quadrupole

to 6 = -52ppm for were

mixture

have been determined.[lO]

of

the

for counter-

and the Na...O

distances.1101

THE ELEMENTS

Presumably interest papers

for

the

reasons

in the elements abstracted

section. appropriate,

no longer

Those which in other

outlined

has declined warrants

in the the

have been abstracted subsections

of

1985 reviewtll

such that

the

the

retention will review;

number of of

a separate

be considered, the majority,

as

4

associated

with

incorporated alkali

in

the

chemistry

the

section

intermetallic

dealing

with

will

compounds,

simple

compounds

of

be the

metals.

1.3

SIMPLE

COMPOUNDS OF THE ALKALI

Experimental

investigations

cations

and

lithium

have

theoretical beeen

subsections

to

cater

the

on

the

chemistry

of

complement Finally,

has

this

1.3.1

of

shown

that

increases

(edge)

in

the

the

the

Following

subsection

binary

necessitated

i.r.

has

been

and

ternary

addition

the

demise

to

the

transferred

here

to

derivatives.

of of

metal

inclusion

devoted

chemistry

studiestlll

hexafluoroanions, the

magnitude

changes

interest

ensure

topics. the

for

that

alkali containing

a

alkali new

metal

subsection

to

Pairs

isolation

salts

levels

these

containing molecules

subject.

Ion

Matrix

pairs

small

compounds

catering

increasing

intercalates cover

for

intermetallic

those

at

elements,

HETALS

ion of

maintained

of

section

of

studies

of

the

of

geometry of

from from

the

Ne or

AMF,

of

the

(A

Ar

(21.

to

The

= K-Cs;

Nz,

of

the

strength

alkali

is As

!I1

to

host-guest

F

(2)

on

latter of

the

metal

a bidentate interactions

/i”\ /“” F

have

dependent

the

coordination

of

metal

M = Nb.Ta,U,Asl, species

interaction

F

(l_)

series

interaction.

CO or (face)

a

condensed

host-guest

a tridentate

interaction

of

5 has been

correlated

bridging

u(C...

sequence

of

correlate

with

0)

formed

have been

spectroscopic M(Li-K,Cs)

during

bases ; the

the

is

and

given

assumed to

interaction

the codeposition

studied

The I:1 exhibit

as Lewis

strongest

and SO,[151

of (i.r.

interaction

metal

atoms

and Ramanf

complexes

weak charge

acids,

alkali

in low temperature

by vibrational

techniques.

to act

terminal

CsClO,;[ll]

separation

host-guest

CO,[141

and NH,[121

appearing

between

> Kr > Xe > N, z+ CO

and NHJ, 1121 CO,!131 matrices

isolated

frequency

increasing

Ne > Ar > Oz * F, The complexes

separation

in matrix

decreasing

with

the

formed

transfer,

Li

K and Cs possibly undoubtedly

between and Na

acting

occurs

as Lewis

in the

Li-NH3

complex. The products four

related Li

of

mononuclear

the codeposition species

to transition

Li(CO),

metal

of

Li and CO1131 include

In = l-4)

carbonyls,

(ii)

atoms and one or two CO molecules

are

only

weakly

bonds

are

using

4-31C

coupled

formed

and (iii)

between

and 6-31G’

and equilibrium

geometries

formed

experiments

in these

Li(CO12($)

exist

two inequivalent (3)

in the

of

the

Li-C-O t 199

with

the

initio lithium

that

=n

groups

chemical

structures carbonyl

species

and

Li2(CO)(5)

adopts

‘x and Sir states.[l61 Li-C-0-Li t ? ‘3d 183 123

? * 14

o-c

1 I 4 182

=u -LitCto 204

true

Li(CO)(Q)

and that

several

calculations.[l61

(5, (4)

with

the electronic

simpler

(it

closely

carbonyl

in which

Ab

of

suggest

zn state

geometries

=3t

species

sets,

are

species

in which

carbonyls.

basis

which

t 166

I I I 126

I I I 164

I12 distances/pm

1:l

N:CO~1141 and H:S02[151

species so=. H2(C02) a C,

are

formed

Whereas adopts

on codeposition

HfCO,) both

and 1:2 H:CO,I151

and M(SO,)

a W-shape

symmetry structure

of

of

alkali

have planar

structure

uncertain

with

geometry.

(M = Na,K,Cs)

metals ring C,,

with

CO= and

symmetry symmetry

(5) tft

and

6

distances/pm

1.3.2

Theoretical

The

number

three

papers

They

reduced.

can,

in

the

species;[l7-211

reaction

intermediates.[29,30] containing

Ab

in

form for

an the

stable

ion

than

intimate

ion

to

6-31C”

basis

(9-1 by

lO.OkJ.mol-‘;I191

(2)

set,

(56.5kJ.molV’)

SiH=-

pairs

moiety

to

be

the

involves the

Carlo

being

the

and

predominate, to

with

simulations that

separated by

Li’ mainly

MBO,

the

ion

pairs

is

stable

than

energy

barrier of

ion

Li’

Calculations

pair

more

to

the

more

SiHJ-Li’,

calculated,

the

to

added;[l81 are

Owing

the

LiSiH,

affinity are

87kJ.mol-x. in

NH,

electroof

Hz0 molecules

movement

other.

of

weight

restricted

of is

suggest

more

(6-1 of more

molecular

derivatives

interaction

interactions

geometry

C,,

low

interaction

solvent

clusters,

electrostatic

inverted

the

as

markedly one

compounds:[22-281

metals

(l&n6281

decreases

is

under

NaCH0.1271

Monte

clusters

pair

larger

favourable the

of

ion-molecule

subsection

considered

reviews:

alkali and

character.1171 NO,-

Li(HzO),‘:

earlier

heavier

the

this

be

Lithium

calculations that

static

still

NaCH&N[26]

initio

indicate

Moieties

for

organometallic

moieties

(M = Na,K),[211

Small

abstracted however,

used

headings

inorganic

of

Treatment

of

using

a

classical

C&

isomer

separating

(g)

and

from based

one on

side

SCEP

of and

the CISD

Li

CEJ)

(2) distances/pm

methods

suggest

bidentate

(C z-1

contrast,

in

that the ground states of LiHgH, geometries.1201

part,

with

earlier

Although

data for

these LiBH,

and LiAlH,

have

conclusions and

LiBH+

which

show

7 ground (CJ,l the

state

configurations

geometries, bidentate

LiAlH,

are

respectively,

extremely

and K, respectively, based

introduction

of

In a separate found

43% (for

bonds

p-orbitels

to decrease

monopolised

The for

ionic

for

M = Li, method,

HMO

the MO bonding character

of

has been

of

M = #a

shown by

to be due to the for

Li-BO,.[211

the M-80,

Kl through

bond has

46% (for

and Streitwieser’s[24,27-291

the

theoretical

analysis

intermediates:

of

the sole

by McKee on the mechanism of

1,2_dilithioethene[221

of

and

Na)

to

groups

have

organometallic exception

is

a

the deprotonation

of

by LiNH,.tSOl

studied, time,

between

LiBH,

from 478 and 480kJ.mol-”

from 49% (for

and reaction

published

ethanol

both

Li1.1211

molecules paper

differences

for

energies

into

the

and tridentate

8.5-25.1kJ.mol-1),[201

to 560kJ.mol-X

study,

(CzV)

in the dissociation

on the extended

Schleyer’s[22,23,25-271 almost

(within

increase

the M-B02 (II = Li,Na.K) calculations

geometries

small

observed

bidentate the energy

and tridentate

experimentally

been

with

the

using

former ab

and 2,3-dilithiopropeneI231 for

initio

1,2-dilithioetheneI221

the

second

methods. using

time,

the

Reoptimisation

latter of

more sophisticated

distances/pm

have been for the

the

first

structures

basis

sets

8 indicate of

that

the

two

the

trans-isomer

cis-isomers

experimental

found

to

be

minima, The

into

(10)

into

both the

first

lithiums

are

potential

minima

a

C,,

symmetry

10.3

and

25.4kJ.mol-’

on

the

the

C,

in-plane process

being

cis

isomer

molecular

of

(14)

adjacent

and

the

of

(13)

in The

one

(16)

lithium

the

(151

in

central

one

of

The

possesses

which

both

the

CH

which analysis

of

two

former,

which

lie a

lithiums

terminal

the of

structures

which

bridging

of

revealed

structure.

latter

state

rearrangement

plane.[221

C2 symmetry

above

to

inversion

state

were

the

2,3-dilithiopropene[231

transition

theoretical

(11)

transportation

about

the

the

and

for

either

recent

earlier

a transition

but

in

with

be

rotation

structure

plane

other

involve

bridged

2-lithioallyllithium

to

the (10)

pathway

doubly

single

have

found

than

with

to

although

was

stable

agreement

in

surface

and

more

bond

step

another

is

contrary

favourable

not

double

I the

(11)

(12)

most

does

carbon-carbon groups

in

but

Furthermore,

structure. (11)

(11.12)

findings1311

conclusions.1321

(10)

lie

carbons

and

carbon.1231

Li

‘\

\r

H-c\cY_ fH ‘H / x 198.

225.3

Li

LCCCI” LLiCLi

1”

121 .o

116.6

119.9

144.8

113.2

133.3

(15)

(14)

(16)

distances/pm

MNDO calculations dimeric

structures

undertakeni cryoscopic studies

of of

to

show

symmetrical

3-lithiopropene

rationalise

measurements which

various

that

and

the variable

whereas

and

unsymmetrical

(allyllithium) results

of

a

temperature

allylsodium

and

have series

been

of

‘Y-n.m.r. allylpotassium

are

9 monomeric

in thf,

The theoretical

allyllithium analysis

exists

as an unsy~etri~al

showed geometry

dimer.

(171 to be lowest

in

energy.1241 Ab initio

calculations

of methyl

radical

reveal

addition

a significant

to ethene

kinetic

acceleration

on complexation.of

the alkene

distances/pm

l-4 (I7_) with the

the

lithium

absence

cation;[251

and presence

respectively. for

alkyl

Extended the

It radical ab

CH&N-,

is

CH,NC-

to a lesser

extent,

next

(2Jl

lowest

H

effects

that

anions

the metallated

in energy

found

geometries ketenimine

with

the metallated

in energy.

Aggregation

the

should

‘N

Na derivatives

lithium

bridged

(181 and forms

(201

nitrile

ylides

and solvation

M-C=N=CH,

lithium

compounds were

probed

The most stable

LiCH,CN

have B-membered ring

and LiCM,NC however,

favours

the

unsolvated

formation

in

be general

M-N=C=CH=

.M.

C-=

energies

k._T.mol-‘,

complexes.1251 the Li,

calculations.[261 Solvation,

activation and 25.1

the effect of

sodium bridged

H.

of

60.2

to alkene-metal

and isomeric

somewhat higher

A

are

examinationi

(191 to be favoured; are

Li’

suggested

addition

initio

the calculated

of

by MNDO dimers

structures of

of

both

(22).

the alternative

of and,

10 4-membered

Hz&

/

ring

Li-C

N-lithiated

ketenimine

dimer

(23).[261

SN

‘N-C

-

Li

‘CH /

HzC

=

Li -NIC

/ \

C FN-Li

(=a)

\ /

CHz

(zb)

/

'N+C-CH,

HzC-CsN'Li' HO' 2

'OH 2 (23)

Ground for

the

state

metal

formyl

complexes

calculations.1271 large

bridged

Such

electronegativity

characterised

by

geometries

are

MCHO (M = Li,Na)

from

Q2-coordination,

which

differences

rather

(24)

long

C-O

between bonds,

also

ab

initio

is

metal

predicted

favoured and

significant

alkoxy-carbene

LiCHONaCHO rlH...Cl/pu 110.4 -

H\ c\

rlC...01/p1 124.3123.9

I

M

0'

rlC...H)/px

190.2

rrn...o1/p1

178.2216.5

UICNI'

65.1'70.3'

224.3

(24)

H\C/Li\O H"S'

H C’L1\O = \,/

H 3C"0

by

carbon,

/\ 0

Hz& (25) Li

is

11 character

in

the

formyl

group

and

predominantly

ionic

M-C

interactions.[271 Optimisation

of

sulphone[28] the

lithium

is

gave

lithium

is

compounds

a

ground

Theoretical ethanol

(3-21C”

basis

setl[301

Reactants

associated

with

and

analyses basis predict

the

monolithium

state

structure

with for

state

interaction

-CH,SO,CH,

(Li’...

of

a ground

calculations

associated the

geometry in

clearly

Similar

oxygen. salt[281

the

resulted

the

the

structure one

is

carbon

of

dimethyl-

(251

in

which

only

one

and

corresponding

dilithium

(26)

each

and

primarily

carbon

salt

in one

ionic

which

In

oxygen. in

both

character

Li+...-CH,SO,CH,-...Li’).[281 of

the

set)[291 the

reaction and

of

of

LiH

with

LiNH,

with

given

in

mechanisms

methanol ethanol

schemes

Transition

Coordination State

and

(3-21+C 1 -

3.

Products

State

H&=0 + Li-H

H AE: =

0

AE = -105.4

AE

Scheme

H

H&

\ /

=

-83.5

AF: = -228.1

1

H& c=o

\

CHz

I

+

3

7

Li-H

Li

HA AS

= 0

As

= -121.3

AE

Scheme

2

I

-86.1

Ax =

-213.6

12

State

State

H

\

c=o

/

H&

Products

Transition

Coordination

Reactants

+ Li-NH,

bE

As

0

=

=

AE = -65.3

-104.6

OLi

/

H&=C

\

H

+ NH, ntz

AE = -231.0

Scheme

(Distances/pm;

are

Energies/kJ.mol-’

-119.7

I

3

quoted

relative

to

that

of

the

reactants)

For

all

very

three

reactions,

similar

in

integrated

population

Li

a charge

carries

same

as

in

1.3.3

ground

quartz

of

ampoule;

cooling silicides silanes K7Li(Si412,

over

4h 12hl

which with

are

protic depend

the

in

state

is

predicted

reactants.[29,301

of

+0.85

state

Li+K

transition

to

analysis of

Intermetallic

Reaction

the

character

Schemes

the

(1)

and

transition

organolithium

to

be

Indeed, (21

state,

indicate almost

that the

compounds.1291

Compounds mixtures

with

heating results

to in

1073K; the

flammable

in

solvents.[331 on

the

silicon

reactant

Nb

4h annealing

formation air

(sealed

and

of which

The

products

molar

ratios.

ampoule

at

red

1073K;

in

a

slow

transparent

form

flammable

formed, Their

K,LiSi, structures

or

13 are

shown

linked

in

by

Each

separate

by

the

lithium

mean

Figure lithiums thus

acts

tetrahedra

lithium

is

remaining

potassiums

Si,

Figure

1.

as

structures

[Li(Si,l,17-

Int.

studies

have

(Raman

active).

unit.

Ed.

been E

Engl.,

In are

caps

a

K7Li(Si412;

corners

of

spectroscopic

K,Li(Si,l,

and both

the

showing dumb-bell

structures,

shown

permission

the

coordinate

and

the

tetrahedra

from

using Angew.

the

hatched Chem.,

25(1986)5661.

completed (Reman

by

potassium

chain

potassiums

(reproduced

two

or

linked shaped

Again

separate

K,LiSi,

are

dumb-bell

Vibrational

of

(258.8-294.7pm;

axis.

edges

of

tetrahedra

symmetry

in

[Li(Si4113-

P,-coordinated

silicons

Sia4-

one

11.1331

polymeric

shaped

only

faces

from

u,-ligands bridge

(Figure

lines

silicons

KJLiSill

act either

Crystal the

six

six

two

on a 3-fold

by in

to

are

~‘[Li(Si,lIJ-. two

a centrosymmetric

six

tetrahedra

chains

to

generate

tetrahedra

bridging

the

Whereas face,

infinite

u,-ligand bonds

located

tetrahedral

the

form a

Si.,4-

hence

surrounded

(271.4pml.

to

the

K7Li(Si412,

atom unit

1Li(Si,l,17lithium

K,LiSi,,

as

and In

272.9pml.

the

In

1.

for

active)

K,LiSi, and

and T,

K,Li(Si,l,;I341

(infrared

and

the Raman

A,

active1

14 bands at

predicted

482,

for

the Sih4-

285 and 356cm-’

The normal equimolar

pressure

quantities

anion

respectively.

modification of

minutes

is

lithium

achieved

in BN or

iron

group

14,/a:

pressure

modification

c = 2328.2 which

crucibles

a = 975, pm), of

a Zintl

(tetragonal;

glass Its

653K) .

ampoule;

structure

2193pm) contains 6-coordinate (Nacl)..

of

the crude

lh heating

.Te = 307.0,331.4pm;

which

structural

type

and LiPb.1351

ratio)

product

in liquid can be

(corundum

crucible

120h annealing

group

crystallographically

each of

I4%/amd; a = 405.3,

crystals

at 773K; space

space The high

LiSn

molar

Single

(trigonal:

three

sodiums

(I:3

NaTea.

of

10

to ambient

phase.

group

of

at 923K

pressure

(tetragonal:

in a novel

structures

sodium and tellurium

by heat-treatment

in sealed

space

crystallises to the

high

by quenching

c = 578 pm) is

ammonia at -223K yields obtained

followed

phase

shows similarities

Reaction

to the

by fusion

argon

at 4GPa and 773K for

pressure

however,

obtained

is

Conversion

by treatment

The normal

conditions.[351

of LiCe

and germanium under

in a molybdenum crucible.[351 modification

43m-Tti) Were observed

(sy~etry

P%f;

at

a = 903.3, c =

independent

lies

on a 3-fold

Na(Of...Te

symmetry axis

= 316.1,324.0pm:

NafS)...Te

= 316.9,319.4pmf./361 L97Au-Mossbauer of

[C222Ml’Au-

spectra

of

MAu (M = Li-Cs)

(M = K-Cs)[371

are

environment

for

the Au atom in all

(M = K-Cs),

but

only

other

presence 1.3.4 Since

of

sizeable

Binary the

starting

field

papers

abstracted

with

for

in nature,

[C222HI+Au-

RbAu and CsAu.

hydrides,

this they

proceeding

s.pectra at

section are

For

indicate

the the

the Au atoms.{371

are

limited

considered

through

and halides,

nitrides

and finishing

in

as a group and phosphides,

with

amides,

and bifluorides.

Schleyer

et al.[381

have

reported

active

LiH,

Finely

suspended

ketone

and 1.1,2.2-tetraphenylacetone

produced

complexes,

gradients

and

a cubic

Compounds

and sulphides,

hydroxides

with

NaAu and KAu. the

electric

number and fragmented oxides

three

two intermetallics,

two intermetallics,

intermatallics

consistent

NaH and KH “superbase” LiH.

capable

by hydrogenating

Hydrogenation

of

BuLi

of

the preparation reagents

instantly at

in hexane

BuNa and BuK, previously

of

extremely

under mild metalating

conditions. dibenxyl-

room temperature, in the

presence

prepared

was

of tmeda.

by reaction

of

15 NerO*Bu

or

with

KO*Bu

BuLi

in hexane/tmeda

reactive

NaH and KH in suspension.

aneously

metalated

completion

oust

Whereas

*BuCOCHs at 253K, the

of

enolate

solutions

formation

the

former

requiring

gave

highly

latter

instant-

was less

vigor-

20 minutes

at

27%293K.[381 The use of

Li,N

Stoichiometric various

reactions

molar

(CpTiCl,), nitrido

as a reducing

ratios)

titanium

As part

of

Baudlert401 phosphides emphasis

and LiJN

and alkali placed

preparation

ratio)

by reaction in dry

was formed, (NaP,CHl

thf;l411

together cleavage All

atoms of

merism.

by nucleophilic potassium,

LiPH,.

both

of

three

cleavage

[421

with

as well

polyphosphides;

thf

white

of

the

single

has also

crystal reported

M3PX9 (M = Li-K1,[421

white

and

(Lip,)

phosphorus

phosphorus

anions

(1:s

was

molar (Nap,)

are

(NaP,CH,l, by metallic

rings

with

number 2 that M,P,,

white

are

phosphorus or

white

phosphorus

of with

(molar

by mesomsodium or

from the

or

l,Z-di-

LizPla

with

sodium of

(molar

ratio

18C6 gives

adduct

ammonia, as well ratio

in phos-

prepared

LiPHz

results

Na 2P 1e as a solvated

reaction

were

iodine

or monoglyme in the presence In liquid

sodium

stabilised

with

also

phosphorus

by

unsubstituted

(M = Li-Kl

Li,P,,

white of

poly-

sodium tetraphosphacyclopentadienide

of

sodium hexadecaphosphide products

metal

specific

using

as from the degradation

Reaction

in boiling

compounds,

alkali

sodium pentaphosphacyclopentadienide

coordination

Li3P7

reaction

CO.[391

polyphosphorus of

from

by the

of

BaudlerI41-441

LiPH 2 with

Na2PICj. (18C61,.2thf.[431 the

formed

determination

as appropriate.l421 of

bromoethane 3:ll

of

hydrogen

The nonadecaphosphides,

reaction

is

and sodium triphosphacyclobutadienide

diglyme.[411

(in

hexanuclear

pentaphosphacyclopentadienide

with

nucleophilic phorus

review

the chemistry

(M = Li,Nal,I411

of

produces

in the presence

techniques. Lithium

LisN

(Cp2TiClz12.

and CpsTi dN3 characterised

in thf

metal

HP,

reduction

Cp2TifCOl,

on structure

of

Na,P,,.143.441 obtained

to

a comprehensive

xrd and 31P-n.m.r. the

with

CpeTi,N

has considered

is

or CpTiCl, in reduction

evidence.

Cp=TiCl,

demonstrated.[391

result Further

clusters

has been

Cp,TiCIZ

in thf

and (CpTiCll,.

mass spectrometric between

of

agent

2:1,

l.S:ll

as Na2PX6, include

1,3-diaminotriphosphane.I441 Single (Li=Pv),

crystal prepared

or Ta crucibles,

xrd

structural

by reaction has revealed

analysis of

of

the elements

a new structure

lithium

heptaphosphids

at 870K in sealed type

(orthorhombic

Nb

16 space

symmetry;

group

P2,2,2,;

a = 974.2,

b =

1053.5,

c *

759.6pm1.1451 The

interalkali

annealing

metal

a mixture

; 6 days

argon

heating

Na,S at

space

(orthorhombic;

KNaS,

sulphide,

of

and

873Kl:[46]

group

has

been

K&S (sealed it

is

by

tube

isostructural

a = 770.3,

Pnma;

crystallised

corundum

under

with

b = 460.4,

PbCl,

c =

829.3pm). The

degradation

of

NazS,5H201[47] phides[49]

and has

involving

been

loss

was

proposed

the

thermal

was

put

of to

leads

to

In

Na,S,

the

of

water

tga

and

of

the

solvated

formate

anions,

air

process

= 0.34

at

.% =

which

is

produced

aqueous

electron

and

hydrogen = 0.12

(Na,S,;

or

of

in

(@(Hz)

polysulphide

either

studies

Na,S

HS-,

HS-

molecules xrd

transformation

(@(Hz) via

pathway

a topotactic

structural = 248nml

to

sodium

pure

the

HS-

evolution

at

X =

2GxC4.61

oxygen

according

to

equation:[491

120,

+

Iodometric

-t

8Na 223 S 0

determination,

chromatography

showed

are

that

formed

Single

and crystals

oxonisation

of

of

(monoclinic:

space

B =

122.34”)

strongly

Rb..

.O

tenth

more

energy

of

packing

magnetic 123Cs)

alkali

of

the

nor

Se

by

099%

ions

by

extraction within

from

1.1491 repeated using

the

c = 876.3pm;

structure,

293.2

to

liquid

structure

b = 602.2,

CsCl-type

ion-pair

polythionates

with

319.lpm

nine

and

a

contact.[50]

metal

halogen

of

a = 645.2, the

and

S03=+

synthesised

varying

has

shielding and

been

followed

PZ1/c;

342.lpm

spectroscopy SOe2-,

consists

resembles

relationship the

have

298K

distances

remote

A linear

sulphur

group

interatomic

x.5,

neither

RbO, at

The

+

vibrational that

the

RbO,

ammonia.[501

the

two

Ha&,

polysul-

dehydration

of

occurs

(as

sodium

then

(A and

by

step

phase

of

and

the

respect

autoxidation

solid and

Na,S.5Hz0;[471

for

presence with

the

results

affording

Aqueous

8Na,S,+,

e7Rb,

of

hydrogen

catalytic

254nm1.[481

the

the

adsorption

of

radical.

undergoes

three

irradiation

light

hydrolysis

becomes

A two

account

U.V.

254nm);[481 by

considered. initially

to

in

solution[481

decomposition

mechanisms.

sulphide

aqueous

rationalise

forward

solution

sodium

in

been

noted

halides

constants f3?1,

between

(HX: of ‘-Br.

the

M = Na-Cs,

the

alkali

1*711

dissociation X = Cl-11

metal nuclei.[511

fz5Na.

and =-K.

A similar

17 relationship of

the

has

alkali

I9F-n.m.r. The

metal

solution

water

attempts

to

maintain

stable

unstable ion

in

the

by

water

hydrogen coordinated

using

or

noted

in

stoichiometry

LiCl

s-butylethylether tetramers

LiX

all

chloride

Na’

ion

comprises

five

separated

an

separations form

stable

in

separations.

are

a

the

hydrogen

the

bonded

to

those

structure

of

Cl-

stable

structures,

rotation

= Cl,Br)

and

techniques

the

in

this

five

observed

aggregates

in

In

not

some

LiI

of the

accessible

owing

to

the

(di-n-butylether, however,

4 _ ,, are

were

aggregates

ethers

i-propyl-n-propyletherl, Li,I,(NCSl

been

dmf.

diethylether;[541

were

ethers.

in

involving

Tetrameric

seen

have

1.4-dioxane.

isopropylacetate.

were

No aggregates

were

stoichiometry

LiSCN thf,

dimethylcarbonate,

solvents.[541

in

and

of

sodium

octahedral

to

(X

carbonate.

these

of

a

probed

n-butylsalt.1551

shell

to

two

no aggregates

chloride

insolubility

at

further

strongly

owing

between

Li,Br,(NCSl

corresponding

the

been

the

The

ions

molecule

spectroscopic

propylene of

At

distorted

cyclopentanone,

any

the

molecules.[52,531

diethylcarbonate;[541

tmurea

the

As

are the

of

coordination

For

has in

simulated. geometry

water

weakened

FTIR

1,3-dioxolane, and

sixth

aggregates

observed

energy

and

molten

dynamics[531

generated.

for

is

temperature

ion.

molecules

water

Dimeric

a

spheres;

bonding

and

the

Cl-

ion-pair.

outer

dissociation

fluorides

halides

octahedral

the is

solvent-separated coordinated

metal

metal

computer

ion-pair

and

replaced

the

solvents1541

and been

an

octahedron

is

earth

3 ambient

have

contact

molecules

between

alkali

structureI

in

a

of aprotic

chloride-AlCl

ion-pair

As

alkaline

structure

solvation

observed

shift.[511

various

pyridinium

water

been and

chemical

water.152.531

The

also

formed

mixed

between

LiI

and

LiSCN.[541 7Li-n.m.r. Cl,

Br,

and

C104-.

potiometric

AsF,-,

chloride-AlCl,

NOsAl

ambient

presence

of

exchange

mechanism.IS51

As

part

al.1561 system

LiCl,-

of have

and

monomers

search

crystal Unlike

of

LiI.CH,OH

of

temperature

for

reinvestigated

the

LiI.4CH,OH. formation

a

studies dissolved

and

fast

Li,Cl,“-

solid

the

adducts

lithium the

molten

of

phase of

salts

salt

indicate

ion

stoichiometry

in

of

highest

diagrams,

X =

the

a

fast

conductors,

diagram the

(LiX;

n-butylpyridinium

dimers

Li’

phase

structure earlier

in

the

l:l,

site

Rabenau

LiI-CH,OH

conducting

which

two

showed 1:3

phase, the and

1:4,

et

18 the

modified

diagram

stoichiometry congruently

322K,

decomposition

and

the

Z(a))

at

structure

contains

1:4;[561

LiI.CH=OH

reactions

In

2(a)).

(Figure 2:3

1:1,

and

and

undergo

249K,

LiI.4CH,OH

2.

Phase

relationships

(bl

projection

of

[Li(CH,0H141+I-

of

peritectic (Figure

2(b)),

the

Li’

ions

(b)

(al

the

of

melts

respectively (Figure

(al

Figure

adducts

LiI.4CH10H

2LiI.3CH,OH

253K of

three

whereas

centres the

of

in

the

crystal

viewed

along

the

tetrahedra

are layers;

x = O.O(thickl

and from

are on I-

Chem.,

Li’

omitted. the

ions The

in

centres

x = 0.75(thickl

are

located

layers.1 Int.

and

of (The

ions

L = O.S(thinl

Angew

system

structure

located the

LiI-CH=OH

(0011.

tetrahedra

x = 0.25tthinl

permission

the

Ed.

on

and the

(reproduced

by

Engl..

25(1986)10871.

are

surrounded

tetrahedrally

[Li(CHeOHl,I+

units

[Li(CHsOH141’ zinc in

and

blende Figure

The

(the

complex

is

and

three

I-

by .O =

ions

in

oxygen

atoms

191.9pml;[561 the

corresponding

structure

unit

cell

with the is

is

formation

of

arrangement

of

similar

shown

by

to

that

broken

the in

lines

2(b)). adduct,

symmetry.1571 and

(Li..

Each

octahedrally acetonitrile

2NaI.3CH,CN.3Hz0, Na’

ion

is

coordinated molecules

located to

three

(Na...N

crystallises on

a 3-fold

water

(Na...O

= 252.3pml.

with

hexagonal

symmetry

axis

= 241.6pml The

sodium

19

centered

octahedra

share

to form continuous contain the

either

faces

with

~Na(~~O)~(~H~CN)~lw

three

nitrogens

two adjacent

chains:

or three

the

oxygen8

octahedra

shared

faces

alternately

along

chain.[571

The structure

of

1090.8,

b = 665.5,

The I,-

ions

305.lpm; iodine

are

the

et

asymmetric

a1.159-611

in high

pressure

modification

nitrogen

[Li(NH21,-1

with

353.7,

increasing

along

charge

For

anions

On warming

chains.

of

hydroxide

anions:

intermediate

discontinuous In the

anions.

high

of

temperature

atoms occupy

are

connected

the

influence

decreases

= of

with

low temperature

bonded

bonds

phase

expansion

was

each Cs atom (Cs...N

the anion

hydrogen

the hydrogen

ammonia

hexagonal

an infinite

the hydroxides, In the

are

the

the Cs atoms combine

surrounding

temperature.[60,611 the

of

which

(0011 to generate

distribution

and with

The Li

.N = Zllpm)

and

summarised

CsLi(NHe1,

the hydrogens,

= 280.3pml;

ten amide anions

are

the metals

xrd data.t591 (Li..

study

amides(591

data

amides,

including

(Li...Li

metal

of

by seven

structural

The structure

390.4pmf.1591

TlI-variants,

the

metal

crystal

edges

the asymmetric

alkali

CsI,.1581

= 363.4-415.8pml.1581

a detailed

by reaction

tetrahedra

chain

chains

of

of

= 283.3,

surrounded

crystallographic

CsLi(NH,),,

by trans-located

with

obtained

from single

distorted

342.3,

a series

autoclaves.[591

of

established

are

Prima: a =

that

(I...1

(Rb...I

have completed

of

group with

bent

geometry

pertinent

were

space

isotypic

the Rb” ions

The interalkali

1.

CsLi,tNH,fJ,

is

and slightly

in an irregular

polymorphism

in Table

(orthorhombic;

c = 971.ipm)

hydroxides;\60,611

the

RbI,

= 178.110);

LIII atoms

Jacobs of

opposite

forming

break

giving

infinite more mobile

transformations the

rocking

are

associated of

vibrations

NaCl-variants,

the anions

the

rotate

quasi-freely.l60,611 The lattice improved data

energies

using

(Table

2)

bifluorides the

bifluorides with the

crystal

structural

details

such that those

between

ionic

of

the

the alkali

auxiliary

decreases

crude

Single

are

exceed

difference

of

revised

the

lattice

calculated

the

bifluorides

energies

energies

with

cation

of

have been The new

data.t621

by classical

lattice

steadily

metal

thermodynamic

of

the

ionic the

radius

models

fluorides

and and

in accordance

models.[621 xrd

studies

formulae structures

of

KF,2.5HF

K2tH2FOllH3F41 of

the

and KF,$HF have

and KIHsF41.[631

IH,F,+,I-

anions

are

revealed Full

given.

20 Table

1.

Crystallographic CsLi(NHzlz. CsOH[611

Compound

parameters

[591

various

CsLi,(NH,),,[591

polymorphs

RbOH,[601

of

RbOD,[601

and CsOD.[611 Symmetry

Temp.

Space

2 a/pm

b/pm

c/pm

BI”

1166.5

577.0

117.4

040.9

-

Group

Range CsLi(NH,l,

monoclinic

c2tc

- 656.4

hexagonal

P6,22

-

orthorhombic

Cmcm

- 875.1

1118.4

545.0

orthorhombic

Cmc2,

4 412.4

1117.6

421.1

-

265-367

monoclinic-I

P2,fm

2 415.1

424.5

603.0

104.5

367-511

monoclinic-II

PZ,/m

2 415.8

427.6

605.4

103.7

511-m.p

cubic

Fm3m

4 608.0

orthorhombic

Cmc2,

4 412.5

1109.9

421.3

-

300-369

monoclinic-I

P2,/m

2 414.7

424.1

600.6

105.1

369-451

monoclinic-II

P2,/m

2 415.5

426.6

603.1

104.2

451-513

modification

513-m.p

cubic

Fm3m

4 607.5

200-498

orthorhombic

Cmcm

4 435.0

498-m.p

cubic

Fm3m

4. 642.7

ortho-

P2,2,2,

4 431.9

CmCm

4 435.2

Fm3m

4 645.7

CsLi,(NH,l, RbOH

15-265

RbOD

15-300

CsOH

for

CsOD

23-230

with

633.4

random

-

-

arrangement

of

atoms

1199.2

451.6

-

1153.8

446.9

-

1189.6

451.2

-

-

rhombic-I 230-460

ortho-

460-m.p

cubic

rhombic-II

The coordination with

independent distances 1.3.5

of

an additional polyhedra in Ternary

To avoid

the

K atoms

fluorine

the

range

and cube-like

is

square

antiprismatic

a square

face

of

in KF,3HF with

one

in KF.2.5HF of

K...F

the contact

269.9-313.7pm.1631

nermanides

unnecessary

above

-

and pnictides

duplication

with

other

Chapters

of

this

two

21

Table

Revised

2.

thermodynamic

data

for

alkali

metal

bifluorides

and fluorides.[621 Li

Na

K

Rb

cs

-bH,“(MHF2(s))/kJ.mol-1

942.3

920.3

927.7

922.6

923.8

U,(MHFzfs))/kJ.mol-l

939

841

753

724

693

-bH,“(MF(s)f/kJ.mol-’

616.0

573.6

567.3

557.7

553.5

U~(MF(s}~/kJ.mol-’

1047

928

827

793

756

review

the

ternary

subsections

are

restricted

and a transition dealing

with

compounds considered

structural and halides, Schuster

germanides[64,651

was normally

Pertinent

treatment

ratios

based

neutron

The dimorphism

of

crucibles.

are

this

elements

in

xrd methods; used.

in Table

using

temperature

for

usualiy

were

summarised

was investigated

oxides,

Characterisa-

or powder

techniquesI

the @+p transition

for both

constituent

crystal

diffraction

LizZnCe

Synthesis the

metal

mainly

have been discovered

in sealed

data

an alkali

papers

and characterised of

on single

crystallographic

methods;[641

five

has prepared

heat

molar

exceptionally

only

both of

have been abstracted

and pnictides.165-671

prolonged

the appropriate tion

a plethora

properties

subsection.

and subsequent

containing

Although

chalcogenides

involved

to those

metal.

in this

both

was found

3.

xrd and tga to be

780(51K. During

an attempted

rubidium

was added

synthesis

in excess:

of the

Rb,As,

R&As,

t was dissolved

in a solution

which

red crystals

~C222Rbl=[Rb(NbAs=)l

In

(271,

only

of

two of

C222 molecules.

the three

The third

[Rb(NbAse112-

chain

Evidently

the

Rb.. .As

compete

not only

also

with

those

observation study

the

with

with

forms

using of

enclosed

anion

in the

Rb’

[NbAsalg-. chains

are

This

to

[VAseIS-

but

surprising

INDO calculational

methods

to

and [K(VAse)lZ-.

Rb and Nb had to be replaced

by K and V for

the

to alter

not thought

able

and ethylenediamine

reasons,

were

from

(271 crystalfised.t681

Although

changes

tube,

not

C222 in ethylenediamine

in the

between

structure

niobium clearly

a one dimensional

Rb’ and C222.

has been probed

product,

Rb atoms are

interactions

between

electronic

of

the complex

those

in a sealed

reaction

technical

significantly

the

22 derived the

energy (As,4p)

3a,

feature

of

Table

level

3.

state

the

which

diagram, with

bonding

Rb(ns,np,l

As-Rb

Crystallographic pnictides

revealed functions

interactions

along

parameters

prepared

for

by Schuster

Structure

that

the is

a important

the

chain.[681

diverse et

Symmetry

coupling

germanides

of

and

al.

Space

a/pm

c/pm

828.6

Ref

Croup

Type a-Li=ZnCe

Na,As

hexagonal

432.6

B-Li,ZnGe

Li,Bi

cubic

614.0

LiLnCe

Fe,P

hexagonal

LiYSn

hexagonal

P62m

64

-

64

731.6

437.3

65

(Ln=Pr,Tb,Dy,Ybl” LiYbBi NaMnX

959.5

763.5

65

tet ragona 1

P4/nmm

408.7

687.6

66

(X=P,As,Sb,Bil’ MMnX (M=Li.K)’

-

NaCu,X,

tetragonal

P4fncc

426.7

617.8

66

CaCu,P,

rhombohedral

FIsm

410.0

2389.3

67

CaCusP,

rhombohedral

Rsm

412.0

2595.6

67

(X=As,SbI’ KCu,X, (X=As,Sbl’ * The

crystallographic

1.3.6

Ternary

Following Hoppe

et

data

oxides

their

containing

two

studies

have

alkali

metals

were

The two more

heat-treatment

in

Cs,K,Cd,0,[7111 appropriate the

third

oxidation Preparative were

alkali of

the details

characterised

information

is

novel

listed

metal used are

collected

of

oxide to

first.

either

in Table

mixtures

a ternary

in Table 5.

and

preparative

routes

prolonged the

of

Rb,NaZn,0,.[70]

NaAu using methods;

Review,[l]

in oxides

involved

oxide

and

the

Rb,Li,,Tb,0,,[7311;

KNa,Au0,,[741

summarised

1985

synthesis

(KLi,Ir0,,[721

produce

xrd

the

Three

common methods

containing

intermetallic using

the

(Na,Li,Mn,0,,[691

mixtures

in

interest

compounds.

capsules

oxides

or

method,

six

sealed

binary

element

their

reporting

of

constituent

the

reviewed

maintained

characterisation employed.

to

and chalcogenides

initial

a1.[69-741

refer

Na,O, 4.

pertinent

involved

controlled

and K202. All

six

structural

compounds

23 Table 4.

Experimental details reported by Hoppe et al. for the synthesis of diverse ternary oxides.

Product

Reagents

Molar

Temp

Anneal Vessel Ref

Ratio

K

'time/d

973

14

Ni

69

Ag Au

72

Na,LisMn,O,

NazO:Li,O:MnO

1:2:2

KLibIr06

Li,O:K,IrO,

3:l

1023

30

2:l

973

27

Rb,Li z4TbeOz-, RbzO:LieTbOe KNa,AuO,

K202:Na202:NaAu

1:1:2

Rb,NaZn,O,

Rb20:Naz0:Zn0

1.2:1.2:1

Cs,K,Cd,O,

CszO:KzO:CdO

LieCoO,

NazO:LiZO:CoO

73

703

6 36

Ag Pt

74

1223

1:l:l

823

17

Ag

71

1.3:1.3:2

853

22

CO

80

70

B-LiRhO=

NanO:Li,O:Rh,OJ

1.45:2.91:1 1223

18

Pd

81

Li,IrO,

Li,O:IrO,

5:l

1098

30

Ag

75

LieIrOLs

LizO:NaZIrO,

5:l

1098

40

75

Li,PdO,

Na,O:Li,O,:Tb,O, 1:3:1

1373

7

Ag Pd

82

LiePtOci

LizO:NaJLiPt,O,

1O:l

1098

100

Au

75

LieCeO,

LizOz:KCeOa

4.5:l

923

63

Li,O,:Tb,O,

6.8:1

1023

13

Ag Au

75

Li,Tb,O, Li,Tb,O,

RbzLil,Tb,O,,

-

1123

25

Au

73

Na,CrO,

NazO:Cr,O,

4:l

1273

30

Ni

76

Na,AuOZ

NaZO,:NaAu

1:l

703

6

77 78

73

NaPrOz

K,O:NazO:PrOl.e, 1.1:1.2:1

1273

2

Ag Ni

NaTbO,

NaeTbO,

1273

10

Ni

78

K,ZnO,

KzO:ZnO

2.1:l

873

30

Pt

70

K,ZnO%

KzO:KeZnOZ

1:l

823

14

Ag

70

Cs,,Cd,Osa

Cs,O:CdO

"2:i

773

20

Ag

79

Hoppe et a1.[70,73,75-821 have also made a very significant contribution to the chemistry of regular ternary oxides, describing the preparation and structural characterisation of 13 materials, Although many of these oxides were synthesised from mixtures containing just one alkali metal oxide (LieIr0,.[751 LisTbZOr,[73] Na,CrO,, 1761 NasAu01,[771 NaTb02.[781 K,ZnOJ,[701 Cs,,Cd,01,[79]l,

24 several metal

were

oxides

obtained

routes

worthy

of

oxides

(NaTb0,[7811

oxidation

those

or

of

binary

(Li,Ce0,[751);

experimental

oxides

were

powder

xrd

Further published

structural

information authors;[83-861

by

oxides

Russian

A novel

are

ion

(fourth)

exchange

has

been

of

a-Fe,O,

a

the

the

composition stable

1773K. on

of

oxides

binary gives

yields

in

studies

method to

is

reactions, K,V,O

14

formed,

(691K1,

chemistry

of

Li,TiOs

contains

spectra

symmetry

of

with

of two

1238

the

the been

Li’

ions

environment

by 20

both

to and

differing

is

responsible

for

5

hours

system[86] which

decom-

respectively. phase

system.

bronze probe

Four

(773Kl

com-

and

K,V,0,.[87] the

structural

LizHfOs.[89]

The

indicate environments; for

diagram

decomposition

KV,Oe

(300~T/K~5201[881 with

30

of

peritectic

vanadium used

are

mixture

1173K to

KVO,-V,O,

(803K1,

variable

the

KzO-RuO,

K,O-V,O,-VO,

K2 V 8 0 21

have

of

modifications

1323K,

the

undergo

Li,Zr0,[89] Li2Ti03

and

reported

which

have

Li,Ti0,,[881

r.

at

the

of

interaction and

heating

for

K,RuO,,

K,Fe40,

compositions

structural

1273K of

and

dta

three

two

reaction by

bronzes

followed

to

the

system[85]

and

whereas

studies

(828101,

together

it

also

of

two

25 hours

K4Ru04

section all

methods

7Li-n.m.

lower

of

have

KV,O,,_,

Spectroscopic

for

heating

Xrd,

All in

the

Li,O-RuO,

synthesis;

reactions

a complex

are

the

from

structures.

produced

KFeO,.

in

prepared

composition of

be

Li,RuO,

exists

of

Similar

authors[871

pounds

of

LieRuO,,

1023K I,

formation

peritectic

to

been

given

layer

kinetics

formed

LieRuO,

the

the

has

described:[83]

approximate

(O.OS
LieRuOs-

the

Russian which

thought

of

LieRuO,-II.

indicate pose

of

Li,,RuO,+,

to

of

it

is

been

LiFeO,

or 5.

are

The

4.

Table

oxides

rhombohedral

phase

initally

formation

depending

has

have

Table crystal

in

details of

oxides

in

single

ternary

ternary

compounds

ternary

included

full

study

conductivity

revealed

the

in

K,C0,;[841 with

electrical

hours

cubic

observed and

using

modification

and

higher

(LisTbz07[7311,

collected

are for

methods

isostructural

A non-stoichiometric

a-Fe,O,

are

data

by

of

or

Others,

used.

intermetallic

characterised pertinent

LizPdOz,[821

oxides

(LisTbz0,[7311 details

structurally

5.

a-NaFeO,

oxides

methods;

metal

(Li,Pd0,[821),

(Na,Au0,[77]1.

were

alkali

similar

decomposition

alkali

two

general,

above

thermal

mixed

metals

In

described

involved

containing

LieIr0,,[751

NaPrOz[7811.

to

comment,

systems

p-LiRh0,,[811

Li&e0,,[751

preparative

Table

reaction

(Li,CoO,,[801

Li,Pt0,,[751

and

from

a

that that

quadrupole

in

25 5.

Crystallographic

Compound

Symmetry

Table

parameters Space

for

diverse

ternary

a/pm

b/pm

c/pm

oxides. 8/-

Fief

Group Na,Li,Mn,O,

Trigonal

R3m

335.6

-

2612.0

-

69

KLi IrO,

Trigonal

Rsm

819.6

-

710.0

-

72

Rb,L i 14TbJ014

Orthorhombic

Immm

1283.1

736.9

-

73

KNa,AuO,

Orthorhombic

Pnnm

1025.6

547.2

400.0

-

74

Rb7NaZnz06

Triclinic

Pi

1128.3

974.5

711.8

-

70

-

71

(114.1” Cs,K,Cd,O,

Triclinic

pi

983.2 (108.3”

790.9

88.5” 918.0 113.7”

106.4”) 653.5 99.9”)

LiFeO,

Hexagonal

295.6

-

1457

-

83

Li,RuO,-I

Tetragonal

537.2

-

1488

-

85

Li,RuO,-II

Tetragonal

617.2

-

1162

L i ,RuO,

Monoclinic

507.8

L i ,CoO,

Tetragonal

P4,lnmc

653.6

-

B-LiRhO,

Cubic

F4,32

841.3

-

LieIrOs

Trigonal

R3

541.5

-

875.5

-

85

984.5

99.9

85

465.4

-

80

-

81

1505.3

-

75

Li,PdO,

Orthorhombic

Immm

375.3

931.6

-

82

LiePtO,

Trigonal

RS

541.5

-

1501.4

-

75

Li&eO,

Trigonal

RS

564.3

-

1620.7

-

75

Li,Tb,O,

Monoclinic

P2,/a

Na,CrO,

Triclinic

Pi

Na,AuO,

Tetragonal

P4,/mnm

970.5

-

NaPrO,

Tetragonal

14,lamd

476.2

NaTbO,

Tetragonal

14,/amd

463.1

K2Fe,07

Cubic

1681

-

KdRu04

Tetragonal

-

1158

-

K,RuO,

Orthorhombic

-

1029

K,ZnO,

Triclinic

1103.3

1056.3

613.5

546.6

109.7

73

859.7

569.8

640.0

-

76

457.8

-

77

-

1096.1

-

78

-

1037.4

-

78

-

84

(124.0”

Pi

(109.7” Cs,,Cd,O,,

Monoclinic

c2tc

298.2

2087.2

98.4”

98.9”)

767.0

-

86

705.4

566.8

-

86

881.3

698.2

-

70

94.6

79

89.6” 674.4

102.4”) 2583.8

26 triplet

and

dipole

singlet

that

in

analysis

Li,Hf0,[891

indicates,

the

for

these

6.

the that

oxides C2/c

A selection

of

lanthanide(III1

Reactants

symmetry

contribution of

centrosymmetric

Table

higher

(relative

theoretical

proposed

the

environment 1:31.[881

vibrational of

the

two

in

a previous group

space

metallothermic

Reactant

of

the

alkali

a

and

(C2/c,

Ccl

appropriate.

of

metals.[931

Time/d

T/K

to

analysis,[901

more

reductions

with

Li,ZrO,

groups

structural is

rise

A group

spectra

space

halides

gives

Products

ratio

NdCl,,

Li

1:l

1123

7

NdCl,,

DyCl,,

Li

2:2

973

7

LiDy&l,,

LiCl

SmCl,,

Na

1:l

1173

3

SmCl,,

NdCl,,

K

2:2

1123

5

KNd&l,,

LiCl NaCl KC1

TmCl,.

Cs

1: 1

873

7

CsTmC 1f

YbBr,,

Rb

1:l

1023

7

RbYbBr,

YbCl,,

Li

1:l

1173

3

Yb,OCl,,

YbCl,,

SmCl,,

Sm,Os,

Li

10:1:12

1173

4

Sm40C1,,

LiCl

EuBr,,

Eu,OJ,

Li

6:1:8

1123

7

Eu,OBr,,

LiBr,

NdCl,,

Na

1:l

1123

7

NdOCl

PrBr,.

Li

1:l

1123

10

Pr,Br,,

GdCl,,

Li

1:l

973

6

LiCdCl,,

CdCl,,

Na

1: 1

973

3

Na,CdCl,,

LiCl

Liz0

LiBr Cd Cd

ErCl,,

Na

1:l

973

9

Na,ErCl,,

CdCl,,

K

1:l

973

10

KCd,Cl,,

LuCl,,

Li

1:l

1223

30

Li,LuCl,,

1:l

773

19

Cs,LiLuCls,

Lu

I:1

773

20

Li,CdClH,“,

K,CdCl,

973

7

CsLu,Cl,,

Li

KCd,Cl,, LuCl,,

Li cs

2: 1

Er K,CdCl,, Lu

Cs,Lu,Cl,.

LuClH,‘, cs,Lu,c1,&

* The

interstitials

reactants

Two

novel

or

ternary

(H the

or

Cl

arise

from

impurities

in

either

by

Klepp

the

containers.

chalcogenides

have

been

reported

et

Cd

27

Reaction

a1.[91,921 at

970K for

space

2 days

group

Pbca;

Similarly,

2 days

of

1.3.7

halides

around

in earlier

their

phase

spectroscopic in turn

Reviews,

for

the

simple

Na,FeS,

yielded

interest

relationships, ternary

Fe and 3

(orthorhombic; ratio

at

NaCu,Tez

in these

these

halides;

molar

c = 2378pml.[921

structural

Each of

Na,S,

c = 2154pm1.[911

R3m; a = 427.6,

properties.

of

Cu and Te in a 1:6:2

NaeTe,,

group

gave

b = 709.1,

in a corundum vessel, space

Ternary

mixture

in a corundum vessel

(rhombohedral;

As noted

a stoichiometric

a = 1194.7,

reaction

973K for

of

compounds revolves

chemistry topics

and

will

solvated

be considered

materials

are

not

covered. and Schleid[931

Meyer

potential action

of of

so-called

highly

(lanthanide) between A,M,X, other

have drawn attention “metallothermic

electropositive

halides.

binary (e.g.

or ternary KGd,Cl,l

refractory

conditions

relationships

RbCl-CeCl,I951

in the KCl-IrCIJ

K~IrzCllo

could

phase

K,IrC1,.[943

Rb&eCi,

system;!951 and RbCe,Cl-,

681 and 889K, for

the

thermal

diagram.1961 congruently

Two ternary

of to

reaction

at 543K; anhydrous

Cs,FeCl,

is metastable

Safonov equilibria (M = Li-Csl

of

dta,

above

changing 1123K to

in the

congruently

at

1019K,

reactions

xrd and spectroscopic Cs,FeC1,,HaO

the CsCl-Feel, exist:

9 which

Cs,FeCl,

polymorphic,

discovered

CsFeCl,,

revise

observed

CsFeCl,

decomposes

does

not exist

at data

and phase

which

melts

in a peritectic and anhydrous

upto 553K.[961

and Hireevl971

have completed

in a number of systems.

is

in peritectic

tga,

chlorides

at 656K and Cs,Fe,Cl

a variety

temperatures

decompose

decomposition

have been used

Cs,FeCl,,H,O

6.

the previously

K,IrCl, at

Dta,

(or

dry and anaerobic

in Table

using

RbCeCl b which melts

respectively.

or

in tantalum

Only one compound K,IrCle

compounds were

which

reactions

in the KCl-IrC13,[941

system:[941

Three

of

the

on metal

MX, (X = Cl,Brl

listed

methods.

decomposing

involving

strictly

systems

not be detected.

at 693K, before

RbCl-CeCl,

products

and C&l-FeCl,I961

xrd and spectroscopic

tga,

under

synthetic

metals)

(Li-Csl

have been studied

was found

give

the

halides

metals

containers

have produced

Phase

(alkali

investigation

lanthanide

and alkali

metal)

reductions”

metals

A systematic

to the

chloride

a review

systems

Two compounds occur

of

including

phase the HCL-PdCl,

in the MCl-PdC12

tM =

28 Na-Csl

systems:

produced

M,PdCl,

is formed

for M = Na-Cs

No compounds

for M = Rb,Cs.

exist

and MPd,Cl,

is

in the LiCl-PdClz

system.1971

Table

Alkali

7.

Compound

I

metal

lanthanide

iodides.

Systems

Lanthanum(III1 M7LnI 1o

Na-Gd

Na-Er

M4Ln17

Li-Sm

Rb-Sm

M3LnI,

Li-Cd

Na-Sm

K-Pr

K-Dy

Rb-Ce

Cs-La

Cs-Cd

Li-Dy

Na-Cd

K-Nd

K-Ho

Rb-Cd

Cs-Pr

Cs-Dy

K-Sm

K-Er

Li-Ho

K-Cd MAn,I

Rb-Dy

Cs-Nd

Cs-Ho

Rb-Ho

Cs-Sm

Cs-Er

Cs-Tm

Na-Nd

Na-Dy

M=LnI,

K-La

K-Pr

K-Nd

MJLn,I,

Li-Sm

Rb-Ce

Cs-Pr

Cs-Sm

Cs-Ho

Rb-Sm

Cs-Nd

Cs-Cd

Cs-Er

Rb-Ho

16

MLn14

K-Sm

K-Ho

MLn,I,

Rb-Ce

Rb-Dy

ML&I,,

Cs-Nd

MLn,I,e

Cs-La

Cs-Pr

LanthanumfIIl MsYbI,

Li-Yb

MYbI,

Na-Yb

Rb-Yb

HYb,I,

Li-Yb

K-Yb

K-Yb

Cs-Yb

Cs-Tm

29

Molodkin

and Dudareva

papers[98-1001 the

alkali

formed

and metal

in

the

Cromov

7.

RbI-CeI,

Twelve

Rb,CeI,

(87930

reaction.

methods;

= Zr,Hf).[l021

Na,CrC1,,[1031

of

halide/binary

Table

8.

Compound

diagram of

(771K1,

been

the

ternary

the

two melt

one

decomposes

mixture

and

or

neutron[llll

data halides

appropriate

binary ill11

are

for

a/pm

were

produced (Li,MI,

Cs,V,Cl,[llll)

diverse b/pm

included

halides

or

by (ll of

a

Using

(NaMn,F,,[10411.

parameters Space

and

be

in Table of

which

synthesised

X-ray[lOZ-1101

Rb,V,Br,,

halide

summarised

crystallographic

the

Crystallographic Symmetry

have

of

either

are phase

compounds,

on

known to

(777K).

using

heat-treatment ternary

the

and RbCe,I,

pertinent

review[lOl]

compounds

systems

Rb&e,I,

The majority

8.

the

reported

halides

original

a comprehensive

three

characterised

diffraction in Table

have

ternary

several

iodides;

contains

novel

structurally

completed

it

in a peritectic

produced

and MI-YbI,

al.1951

system;

congruently,

have

lanthanide

MI-LnI,

et

have

ternary c/pm

halides. B/O

Ref

Group Li2Zr16 Li,Hf

Ig

cubic

Im3m^

1358 1357

102

cubic

I m3m’

monoclinic

P2,fc

541.4

Na&rCl,

trigonal

P5lc

682.0

Na,MnFs

monoclinic

P2, /c

771.9

523.6

1086.2

NaMn,F,,

orthorhombic

Fdd2

1318.1

1561.8

730.9

KCrF4

orthorhombic

Pnma

1576

743 743.2

LiMnFa

102

KCrF4

orthorhombic

Pnma

1573.2

K,CdCl,

trigonal

R%

1210.5

Rb,V,Br,

hexagonal

P69/mmc

Rb,CdCl,

trigonal

R3’c

Cs,V,Cl,

hexagonal

P6,/mmc

Cs,CuF,

tetragonal

14/mmm

* Alternative

space

groups

462.9

113.2

1203.4

736.1

107 103

109.0

109 104

1838

105

1833.1

106

1490.9

110

1853

111

1557.0

110

724.0

1795

111

440.3

1403.2

108

1243.9

are

569.4

1432

and

IT3m.

30 similar

heat-treatment whereas

KCrF4; PbCl,

to

1203K

et

a1.[1061

at

1023K

routes of

a

for

followed

60

were

also

worthy

Cs,IrBrs

has

of

with

completed[ll31

and

as

been

Five been (a

mixed

alkali

reported.

the

vessel.

Cubic

1087.3pm)[1171 of

773K; Single

former

days.

followed

copper

in

metastable

Cs,KCuF,

ratio)

annealing

(X

in

at

(a

and

a

heating

fluorine

under

and

at

has

been

have

Cs,NaFeF,

obtained

by

from

the

2h.

in

and

Cs,KScCl,

a

platinum

with

(a

=

lithium

vessels

at

temperature. were

obtained

a CsCl:KCl:CuO

atmosphere

argon

CsNiBr=.

structures

= 889.4pm1[1181

by

spectra

= Cl,Br)

tantalum

room

been

of

CsLu,Cl,

welded

have

prepared

for

of

arc

M = Cs.

n.q.r.

713K

for

at

653K

for

100 days

in

vessels.

Halogen single

by

reaction

manufactured

molar

X = Cl:

phases

previously 1Oe Nrn-=

of

been

absorption

(Fm3ml

1040.9pm1[1171

by

is

cubic

powders,

(2:l:l

=

potassium

product of

30 x

(a

prepared

with

crystals

mixture

at

also

CsNiCl,

pressure

is

and

( a = 824.4pm1[1121 high

to

iodination

presence in

cubic

variants,

Cs,LiLuCl, were

annealing

523K

and

the

with

route

Cs,ZnBr,

CsMg,_,Ni,X,

of

metastable

pressure to

Cs,Sc,Cl, the

halides

elBr

of

metal

analysis,

have

of

established

Rb=LiFeF,

are

normal

fluorides,

ordering

crystal

Cs(Cl,Br), form

Cr,C1,Br,J-

in

xrd

methods.[ll9,1201

to

metal Cubic

binary

was

synthetic

M = Fib,

luminescence times

(lO&T/KC273);[1151

= 873.9pml[1161

and

crystal

either

solution

repeated

times

tube

alkali

regrinding

X = Cl;

Hoppe gold

aqueous

analyses

relaxation

transfer

by

dependences

decay

determined

prepared

(M = K,

a mixed

vibrational

intermediate

temperature

Single

energy

heating

by

M,Mo,X,

of

The a

a

and

preparative

from

of

623K. in

decomposition

or

spectroscopic

luminescence

excitation

was

with

quadrupolar

measured.11141

thermal

subject

it

433K

The

frequencies

have

at

for

X = C1,Br.I).

well

the

to

CrF,

interesting

(M = K,Rb1[1101).

been

Vibrational

repressing.

other

produced

of KHF=,CrF,

h-l)

and

crystallisation

note;11121 NaI

(6K

KF,CuF,

(LiMnF4[10711

and

independently

a mixture

cooling of

included

halide

M,CdCl,

which

slow

these

ternary

heated

Several

days.

employed:

(NazMnFs,[1091

as

by

a mixture

(Cs,CuF,[lOBl),

Cs,IrI,.

two groups

methods, et a1.[1051

annealed

higher

halide

Dewan

layers isolated units)

Cs,Cr,Br,Cl,

and

spectroscopic

Its with pairs of

structure chromium of

which

(optical, is

based

atoms

face-shared bromine

investigated

using

vibrational) on

ordered octahedra

selectively

closest in

packing

octahedral (i.e. occupies

of sites

binuclear the

12

31 terminal Very

halogen small

PZ,/c,

positions

quantities

a = 672.6,

on heating

with

(57.OKl

are

spectra

comparable

annihilation

of

side

(monoclinic,

c = 739.lpm.

the principal

temperatures

optical

mixtures of

of

bands

which

almost

KCrF,

f55.OK1

Rb,CrCl,

compounds are

group

were and K&rF,,

1203K.~105~

Rb,CrCl,Br

40 that

both

products, to

space

p = 125.3”)

and Rb,CrCl,Br,

(52.4K1;[1211

dominated vanish

the

by two magnon

at

low temperature.

Intsrcalates

Owing to their a rapid of

K,Cr&l,F,

KHFZ,CrF3,PbC12

The Curie

1.3.8

of

one end only.

b = 1115.7,

together

obtained,

at

alkali

intercalates

subsection

A convenient cations

reducing

agent

formation

of

layered

+

In the majority

of

solid

they

were

Theoretical[l231 molybdenum[l231

+

devices.

the

need for

a

alkali

MBH, (M = Li-Kf

anion

occurs

the

structure

acts

with

as the

concomitant

cell)

the

the material

derived

cell

single metal

preparedll251 (773
tungsten

from binary

containing

of

have been completed. has been

band calculations readily

dimensional

on a number

rationalises

the

conductor.

The

shown to be hexagonal, neutron

bronzes, oxide

significant

9.

Mo.30H003 (M = K,Rb)

a = 738.9,

and characterised

conditions

studies

band structure

crystal

without

in Table

bronzes

is a pseudo-one

parameters

clearly and the

when normalised to M,MoSoO,, (i.e.

K0.26 WO, has been

time-of-flight

proceeds

is given

of

fact

of

Hz

intercalates,

tight-binding

half unit

unit

of

obtained,

and slabs;11231

structure

+

reaction

and tungsten[124,125J

by performing

P63 with

I&%

a list

of model chains

Products

using

the BH,-

and experimental[l24,1251

The band electronic

mixed alkali

hence

intercalating

matrices

intercalation

cases,

under

that

storage

to the chemistry

topic.

method for

ZM,'IA"-1

byproducts:

examined

energy devoted

B2Hb and Hz:

undesirable which

this

published:[lZZ]

and cation

2A

+

to cover

into

has been

papers

can be perceived:

straightforward

reagents

ZxMBH,

in high-density

in the number of

metal

separate metal

importance

increase

X-ray

diffraction

H,K,WOs

mixtures

space

group

c = 750.8pm from data.

(H = Li,Nal

in closed

The

have been

vessels

by xrd and sem methods. amounts of

lithium

or

sodium could

32 A hexagonal

not be prepared. and

Ix+y1<0.33;

prepared. Four

xaO.45

distinct

and 4)

9.

phase

forms

with

lithium

sodium derivative was obtained

with

for

could both

x>O.l9

not be

lithium

and

and Ix+yl
rhombohedral

have been

electrochemical Table

corresponding

A tetragonal

sodium for 3.8

the

phase

phases

(Li,Mo,X,;

identifiedllZ61

intercalation

Intercalated

of

products

X = S,Se;

as a result lithium

into

of

the

x = 1,3,

the

Mo6Xe iX = S,Se)

synthesised

using

MBH, (M = Li-K)

tAI:IBH,-I

Time

TJK

reagents.[l221 Compound

Solvent

Color

ratio

MxIA”-I

Li 0.76M003

ether

1.0:80

12h

298

dark

Na,.,&ioO~

i -PrOH

l:f

5h

338

blue

Nao_e,fH~01,.,,MoO,

wet EtOH

1:11

6h

333

blue

K o.-,xM00s

i -PrOH

l:].

12h

338

blue

Li,.,,Vz05

ether

1:l

4h

298

dark

green

Lio.47V,05

ether

I:1

3h

298

dark

green

LifH,Ol,FeOCl

wet ether

I:13

2h

298

black

Nao.e (MeOH1o.sFeOCl

MeOH

I:1

2h

298

black

Ko.zaFeOCl

MeOH

1:0.9

2h

298

black

L i o osTaS2

pyridine

1:1.9

6h

338

metallic

pyridine

f:5

10h

338

gray metallic

Li 0.17fH20)o.4TaS2

wet MeOH

1:3.5

12h

298

gray metallic

Na o. 40TaS2

pyridine

1:1.4

22h

338

gray metallic

Nao.4(H2014TaS2

wet

X:1*4

22h

338

gray metallic

Li,Ti&

EtOH

1:l

22h

338

metallic

pyridine

6-y gray

host

lattices

by cathodic

LiJLiCl04,propylene

blue

reduction

carbonateJMobXe

in the galvanic (X - S,Se).

cell:

33 The

results

data

are

indicate

formation

that

of

the has

n-butyllithium

evacuated

Table

transfer

occurs

in

suggesting Li’

ions

by

reaction tubes

for

Li,Mo,X,

the

at

with

to

be

rhombohedral

of

Schlenk

Li,Mo,S, the

appear

A similar

lattice

(X

1

the

7Li-n.m.r.

systems.

MoeTee 298K

phase,

with

for

5 days.[1271

intercalates[126.1271

10.

Rhombohedral

X

two

clusters

produced

parameters

Li,Mo,X,

the

intercalates.

been

in

10.

charge

[Mo,Se.12-;~1261

in

collected

for

(Li312+

other

Crystallographic

Table

partial

Lie=+ in

Li,.,Mo,Tee,

are

similar

triangular

formulation, “normal”

closely

parameters

of

lithium

intercalates,

= S.Se,Te).

3

3.8

4

3.5

Se

Se

Se

663.8

659.6

664.7

672.4

691.5

692.3

706.2

alo

92.55

94.29

94.23

94.52

92.23

94.43

94.40

92.52

The

intercalates

= Sc,Y,Cd; stoichiometric tantalum

or

lattices

niobium

Lithium

chemically were

To

but

at

IONS a

for

sub-divisions and

importance:

are

considered

is

metals.

logical this

or

the

(A

= Li-K; by

H,),

M and

those singly (A

AX in

Although

atom

the the

heavy

structures.

atom

M = Ti,Zrl phases

and

host

and

containing

doubly

= Li,Nal (Ti(IVl

M

sealed

structure,

= Li,Na;

for

MXH,

and and

lithiated NbTiP,O,,

Nb(V1

can

but be

inert).

format

to

METALS CONTAINING

for the

the

sub-divisions there

cannot

associated has

are

subjects

which

been

ORGANIC

presentation

majority

specialised

remainder,

Since

(A

synthesised[l281

ZrBr-type

unreactive

section,

devoted

in

heavy

ATi,P,O,,

were

lattices

Te

been

1023-1173K.

achieved

from

Zr(IV1

provide

MHz (or

species;11291

= Li,Na)

COMPLEX

host have

AM,P,O,,

be

COMPOUNDS OF THE ALKALI

abstracted

alkali

MX,,

ZrCl-

into

only

prepared (A

their

ZrBr-type

the

reducible

AZr&‘,O,,

1.4

either

could

reduced

the

insertion

NbTiP,O,,

of

vessels

adopt have

and

x = 0.6-0.71

reaction

intercalates

phases

A,MXH,

X = C1,Br;

S

3

646.7

S

S

1

a/pm

X

S

4

but

of

the

reviewed

in

of be with

little

MOLECULES

current

thus the

data

interest

categorised. individual

change

in

OR

34 priorities

during

subsections

1.4.1 The

Raman

of

the The

molecular of

zig-zag

adopted

chain structure

polymeric

for

complexes by

which

band,

the

sequence

the

1985

of

polyethyleneglycols intense

can

indicates

be

a

nearly metal

of

1:l

adduct

of

of

NaI,diglyme The

as

useful ordering

cation.

NaI

units

sodium

a

band

symmetric

alkali

chains

with

polarised

used

the

(281.11311

review.[l]

an

around the

of

Ionophores

characterised

formation,

arrangement

months,

Lipophilic

This

complex

that

liquid

are

polyethylene

consists

to

of

salts

eighteen

Acyclic

860cm-l.11301

monitor of

of

spectra

metal

past

identical

Complexes

alkali near

is

the

with

diglyme

built

atoms,

up

which

in

a

are

I

located

on

316.4pml

Z-fold

and

242.7.271.4pm) of

chelating

ligands

organic

the

ion

Enhanced

model

to

radical

anion

The

extraction water

I

such pair

into

both

the

the

iodine

diglyme

octahedral

bonds as

by of

(Na...I

molecules

arrangement.

is

surprising

snce

diglyme

normally

=

The

complexation

results

=

(Na...O

in

with

“solvent

formation.[l311 and

membrane

transport (O.lM

of

mechanism

Li’

obtained

higher

Li’

of

M’

spectrophotometrically;[l331

in has

the by

via

through a

an

novel

demonstrated.[l32]

(291

membrane,

has

very

the

limited

corresponding reduction,

rates.[1321

(M = Li-Csl

and

using the

cations

CH,Cl,l

been

electrochemical

transport

dichloroethane

metal

podand

across

(al’,

alkali

“Bu,NClO,

anthraquinone

transport

much

bridged

oxygens

distorted

neutral

ability

from

a

switching

the

exhibits

are

the

Na...

binding

electrochemical Whereas

of

in

retention

separated”

axes

two

M2+

(301

observed

(H has

= Mg-Bal been

extraction

as

halides

studied sequences

are

35

K' > Rb' > Cs' > Na' > Li'

Ba2'

Structural

> Sr2+

> Ca?'

> Mg2+

data have been published

for the

lithiumll341

and

HO

(cH,),CCH,C(CH,),

0

OH

49 :I

1;

Oo~“woCH= 3

(29)

OH

(31)

‘,I a

0 R = Me.“Bu

0

36 calcium[l351 The

salts

lithium

salt,

is

four

205.4pm)

and

polymeric,

manganese

salt.

bipyramidal oxygens

is The

of

a

chelating

oxygen

water

by

two

oxygens

and

two

water

atom

is

sphere ligand

from

molecules

a

a

=

from

ligand

(Ca...O

=

194.5,

(35),[1351 with

the

a pentagonal

four

equatorial

= 230.8-252.1pm),

ligand

= is

ligands

(Li...O

in by

(Li...O Li(2)

separate

isostructural

positioned

whereas

geometry

196.7pml,

molecules

and

a

atoms;

[(~),Ca,1,4H,O

provided

second

(Ca...O

chelating

(Li...O

isomorphous Ca

is

Li

coordination

of

salt,

(31).

which

independent

molecule

calcium

coordination

equatorial axial

oxygens

193.1,198.4pm) The

two pyramidal

water

coordinated

=

is

square

axial

197.7pm).[1341 which

a

equatorial

an

tetrahedrally (Li...O

in

acid

(34),[1341

contains

dimer,

located

comprising

benzene-1,2-dioxydiacetic

[(~)zLi,1,6H20

centrosymmetric Li(l)

of

(Ca...O

a

= 245.lpm)

fifth and

two

= 233.4.239.8pm).

0

A

0

b I

I

OH,

'CaLO

O’ I\ I

0

0-Li(l)

0

/

I

A series

of

substitution None

of

the

\

ionophores. of

the

aromatic

substituents,

electronegativities

based

(-CHs,

ring despite -0CHe.

on

(32)

have

carrying

been

the

their

widely

-CHO,

-CN,

prepared

ether

by

oxygens.[l361

varying -NO,.

-Br)

have

a

37 discernible

effect

= Li-Cs)

and

on

M2+

the

(M = Mg-Bal

Na’

> K’

BaZ’

The in

ionophores

the

of

The

crystal

structure

the

Li

to

atom

ligand

0 =

(Li...

the

anion

the

Li

be

(Li..

atom

> Hb’

in of

vary

the in

> Cs’

> Ca2+

exhibit

Na’

of

which

> Sr2’

(33)

presence

selectivity

four

.N

= 203.2pml

in

76pm above

a

the

version)

and

square

plane

of the

pyramidal

of

the

Li’

membranes.11371

oxygens

195.0,197.9,208.5,222.9pm)

lies

for

liquid

(methyl

the

(M

sequences:

selectivity

lipophilic

by

M’

Mg2+.

>

[(33lLil+NCS-

coordinated

the

for

> Li’

remarkable

highly

ionophores

shows a

chelating

nitrogen

of

arrangement;

four

oxygens

of

the

ionophore.11371 The

flexibility

coordination

of of

[(~l,Li,l,6H,O been

its

heteroatoms oxygen

of

type Li

of

small

and

[(331Lil+NCS-.

structurally

occurs,

this

the

ionophore

atom.

As

pyramidal

of

the

ionophore

anion

(Li...O

the

Again geometry

a

0

/N

\

= 217;

atom

strongly

of

H+

(M

bombardment followed

Competitive

Li...N

Li

atom

four

=

bn’)

N

by

ethers

(371,

is

sizes

than

(12C4.

capable

mass K’

0

121pml

0

the to

crown its

Na’;

(371

it

binds

experiments, 18C61,

complexing ethers;[l391

flexibility.

by

has

been

spectroscopy.11391

and

15C5,

of

Li-Cs)

=

complexation

crown

attributed

the

and

an

3

N\ /

Complexation fast

-

0

been

= 200pml.

tYx3 -

has

five-coordinate

comprising

(Li...O

favours

as

[(3&)Lil+CiO,-

analysed.[l381

square

obviously

well

It Rb’

between

for cations the

these of

examined

and

binds Cs’

(371 -

versatility

Li’

but

and

cations, a much

by

a

series

indicate wider of

of that

range (371

most

weakly.

can

of be

38

1.4.2

Crown

As of

in

the

Complexes

previous chemistry

crown

ethers

for

split

into

four

crown

ethers

ethers,

involving The and

the

are

alkali

to

1:3

with is

observed

complexes 1:l:l thf

have

complex ,

metals

vibrational

for

18C6 with

host:guest

of

by

ethers

The

and

studied

18C6[1431 by

complexed,

12C4

forms

adopts

forms

Fourier

transform

solution

(CHCl,)

All

of

a

the

potassium macrocycles

for

ratios DB18C6

host:guest

other

for

both

for

Host:guest

a

K+

oximates)

the

NaNCS,

KOPh;

1:l;

and

been

macrocycles

the

1:l.

NaOPh.

been and

on

of and

ratio

isolated

DB18C6 solvent

with

NaNCS

molecule

solid

crystal

with i.r.

with with

Ds,.

spectroscopic structure

and

using

single

a

fdme,

II”

or

C,,

occur

(M = Li-K) Raman

with Cq

Ci

C,

the

have

symmetry;

D4 symmetry or

in

spectroscopy. when

and

symmetry.

studies[l441 of

alkaline

both xrd

which

and

conformations

state

alkali

changes

using

conformations

infrared

of

effected

complexation

conformations

and

Na+

tendency

for

with

conformational

adopt

ligands

the

little

complexation has

authors

both

18C6

the

Russian

When free,

detail.[l401

has

containing

of

in

obtained.[l411

analysis crown

of

tendency

incorporation

is

in

solvents

with

of

he

preorganisation

containing

but

than

ratios

spectrscopicll42-1441

1264[142]

is

DCH18C6

complexation which

thiocyanates,

DCH18C6

for

methods.[144-1481

been

and

and

relationships

absence

solutions

and

1:3-dioxolanel

earth

ethereal

greater

18C6

involving

Structural

from

no

the

the

covered

(phenoxides,

ratios

NaOPh

are

there

design,

in

molecular

complexes

virtually

from

for

of

molecules

of

the

‘classical’ lariat

unusual

review

of

in

solution, and

observed

DCH18C6 of

in

host:guest

are

DCH18C6

salts

isolated

have

1:2

role

been

discussed.

cations

Although

complexes

complexes

are

of

(if

(ii)

Structure-bonding

a variety

or

of

of

been has

topic

complexes

aspects

complexes

have

derivatives,

organic

the

potassium

aggregated

which

extensive

metal

of

DB18C6

and

sodium

an

metal

the

ligands

synthetic

described.El411 sodium

in

process.

synthesis

18C6,

Consequently

ionophores

emphasises

complexation

earth

describe

ionophores

substituted

written

which

alkaline

macrocyclic

designed

particularly the

their

product has

by

and

macrocyclic

review.

novel

natural

publications

subsections

and

Cram11401 cations

alkali

related

this

(iii)

(iv)

of

and

abstracted

many

years,

of KNO,

the

complex

of

39 the

2,6-dimethyl

is

similar

of

the

derivative

in

solid

the

two

state

which

(K(l’l,

K(2)

(K(l)...0

are

and

= 276.6-286.8; has

a-fold

D,,

of

crystal

xrd

contain

two

spheres

The

very

to

the

of

the

nitrate

methyl

are

in

the

located

are

of

above

the

ligand the

completed

(K(l)...0

two

heteratoms

substituents);

K atoms

anion

analysis[l441

coplanar

.O = 276.0-309.8pml the

structure

K atoms

similar,

coordinated

(ignoring

a bidentate

to

the

by

two

= 278.6,279.8;

.O = 272.8,285.5pm).[1441

K(2).. The

isomorphous

crystal

structures

a

Three

the

(Fig.

3(a)).

All

conformation;

two

the

4-fold

rotation three of

cation,

included

in

the

Single

orientation,

axis

forming

a

12C4 molecules form

channel

xrd

while

structural

[18C6Sr12+[(8uOl,P0,1z-.H,O

molecules. the

crown

two

oxygens

ether

independent,

The ether

conformation opposite

a water

heteroatoms with

ends

the

tilted

Sr

of

atoms

towards

in

cations The

are

a

Sr (PC

letter:[1471

no

which

of

the

cation.[l451

oxygens

of

the

the

by

a

base

the

=

crown

Sr(21...0

=

pseudo-boat and

The

with

structure

= phthalocyanine) of

of

(Sr(l)...O

side

adopt

from

two

= 273-281pmI.

= 262;

ring

of

six

atom.11461

details

is

two

anions

on each

“60pm

the

ring complex

similar,

Sr(2)...0

18C6

C,

presence

by

(Sr(l)...O

the

[18C6Lil’[18C6Li~thf,1‘[FePclzreported

the

structurally

one

same

the

but

dibutylphosphato

molecule

structure

free

revealed

= 267-281;

which

of

coordinated

.O = 243,250pmI

and The

are

monodentate

Sr(21..

261pmI.

atoms

(Sr(lI...O

of

ring,

Sr

by

of

type

3(b,c)i

is

by

stacked

structure

(Fig.

third

each

the

analysis[l461 has

crystallographically

have

formed

the

and

are

channel

sandwich

(M = Li,K)

hydrophobic

crystal

a 2:l

inclusion

determined

molecules

similar

them

molecules,

been

with

[(12C4),Ml+

Y-cyclodextrin

macrocyclic

have

Y-cyclodextrin

12C4 mnolecule

along

241,247;

the

(3:3:1:231

(3:3:1:271

analyses.11451

includes

with

of

Y-cyclodextrin.12C4.LiSCN.Hz0

complexes,

Y-cyclodextrin.12C4.KCl.Hz0 xrd

it

that

complexes.

K(2)..

symmetry

coordination

oxygens

A single

structurally

64pml

indicate

shows

distinct

complexes,

which

18C6

phases.

structure

crystallographically

66;

of

has

structure

of

been the

provided.

crystal

structure

crystallographically molecular

units.11481

(K(1),18:

K(21,7pmI

of

[DB18C6Kl’NCS-

independent In and

are

both

yet

contains

structurally

molecules

coordinated

the to

the

two similar

K atoms six

lie

coplanar

above

40

(al

C

Figure

3.

The

channel-type

12C4.LiSCN

structure

(3:3:11

molecules

are

omitted

for

(al

inclusion

shown

by

clarity,

full

and

Y-cyclodextrin.12C4.Li’ 12C4.K’

(cl

are

plotted

full

and

by

in hatched

permission

the

space

from

J.

and

anions

12C4 are

of

Y-cyclodextrin.-

(M’

filling

circles,

(Li’ SCN-

structures and

complexes

the

Y-cyclodextrin.-

circles:

(bl

(2:2:11

of

complex

and

12C4 molecules

mode,

indicated

by

respectively)(reproduced Am.

Chem.

Sot.,

109(19871

24091.

oxygens

of

the

ether

266-283pml. the

The

K atoms

= 280;

are

K(2)..

[DB18C6Kl‘XC,H,OH

and

(K(l)...0

completed

by

= 269pml.[1481

(X

= NCS,Br,I,NO,l

CHCIJ

undergo

have

melts partial

been

= 262-283;

pyramidal

.N

IDB18C6KI+NCSmelting

ring

hexagonal

the

nitrogens The and

determined

congruently, dissociation

K(21...0

coordination of

thermal of

some by

dsc

the

anion

of

their

of adducts

methods.

their

(X

=

of

(K(ll...N

stabilities

IDBlBC6KI+Xinto

=

geometries

with

Whereas I,NO,l

components.

when Of

41

the adducts.

[DB18C6KJ’I-.C2HsOH

dissociation,

but

components

[DB18C6Kl+Br-.3CHCl,

U.v.-visible[149;1501

U.V. -visible stability

of

spectral sequence

data,

of

the

[DBSOClOKI’ not differ of

>

with

the

1:l

independent 39K-n.m.r.

constant

of data

of

K’ with Popov

Monotonic solvent

of

>

From

have shown that H’

(M = Na,K)

the

with

IB15C5Nal’ and that

Mz+ tK = Ca-Baf

the

with

stability

DB30ClO in

have been used complex

studied

al.11541

with of

which

the

the

reported

constants

l,lO-diaxa-18C6

of

solutions

respect

to the

size

in binary constants

solvent

and the nature authors[l%-1611

of

the

solvent were

acetone,

methods

to

systems.

observed

for

all

the

acetonitrile,

or hmpaI1521 and dmf with of

the

pyridine-methanol

variation

solvent

is

with

and Ba2’

ligand

the

binding

have considered

with

of

18C6.

and propylene

and a single

The results cation,

to a Popov

determination

acetonitrile

two cations of

attributed

composition.

the simultaneous

methods.

and charge

complex

in nitromethane.

spectroscopic

H” (M = Li-Csf

containing n.m.r.

complex

the 2:l

Cs” by DB21C7.[1521

and C222 in acetone,

competitive

1:f

the exception of

formation

B30ClO in

n.m.r.

the observed

structure

the

have shown that

lJ3Cs

pyridine

have also

formation

K’ with

(dmso with

with

for

in the

Several

of

to calculate

studies

in formation

carbonate,

system11521

[DB30C10Ca12+

>

solvent.

and DB27C9[1531

systems

carbonate

[DB30C10Balz’

the complexation

acetonitrile[l531)

using

al. of

concentration.

have applied

changes

propylene

>

similar

DB24C81152.1531

the

parameters

by crown ethers.

mixtures:[1491

[Bl5CSKl+

DB30ClO coexists

et al.

investigate

et

et

complexes

solvent

the 2:l

nitrobenzene;[l511

change

its

spectroscopic

thermodynamic

Cholivand 1:l

complexes

[DB30C10SrlZ’

of

into

dmf and dmso:ll501

CHSOH,

is

dissociates

and Hz* cations

M’

B15C5 or DB30ClO in CH,CN-H,O

does

without

and n.m.r.[151-1541

have been used to determine

the complexation

sequence

the ethanol

on heating.11481

techniques for

loses

are

anion

discussed

solvating

ability

with of

groups.11541 diverse

aspects

of

the

42 extraction

of

solution

into

theoretical two

alkali organic

method

phase

of

method

published Extraction

constants

(M = Ca-Baf

in

ether

f15C5,

C2221

complexing

systems M2+

in

the

the

at

selectivity

18C6)

separation Rb’

of

(using

also

be

The

of

(and

experimentally

of

(381)

In

the

6 position

the

extraction.

and

of

of

M’

(M = Li-Csl

(1.1,2,2-tetrachloroethanel

has

been

elucidated[l591

and

membrane

ring:11591

is

the

of

and

correlated

rate

of

the the

with

into

and

study,[1581

the

and

sharp

DB19C6

increase

and

the

(391,

of

Ba2+

in

unlike

presence

(3915, -

transfer

experimentally

concluded

preferable are

the

of

Na’;

from

K’

(using

(3911 -

the

can

has

as less

mobile

of

ion

been

uptake,

hydrophobic

in and

the

liquid

which

of

DCH18C6

release ligands

in

cations (the

flux

anions). K‘

or

(as

picrate)

DB18C6, the

and

its of

presence

from constants and which

membrane form

the crown

the

anions

extraction ion

the

hydrated

the

interface

of

of by

assessed11601

macrocyclic

carriers

size

extractability

liquid-liquid

the

of

carrier

as

coefficient

weakly of

number

a H=O/CHCl,

liquid

selectivity

the

of

18C6,

a

DB18C6

determined

flux

lyotropic

ligands

that

The

hydration

containing

across

through

distribution

by

is

(the of

between

rates

flux

mainly

cation

determined

measured

transport

however,

degree

CHCI,

macrocyclic

was

and

and

ring

(381

(381

CaZ’

iC221,

H=O-CHCI,

various

a

M2+ crown

(M = Li-Cs)

DB16C5

in

or

measurements.

flux,

relationship water

which

by

well

from

It

in

M’

in

(381 -

salt

controlled

salt

hydrophobicity

was high)

from

cryptand

containing

from

potential

transport

these

the

Both

from

membrane

The

latter

into

for

diverse

effected.Il581

mechanism

cation

and

the

results

fusing

of

of

containing

K’

cryptands.

determined

for

of

for

predictively.

presence

and

extract

SF’

used

DB-6-hydroxy-16C5

group

Na”

and

fM = Na-Csl

M‘

systems

hydroxyl

from

the

18C6[1571

(DB16C5,

be

A

a variety

DB30ClOl

for

selectively

Li‘

in

DCH24C8,

H,O-CHCl,

the

can

systems

(391).[1581

of rings

DB16C5

have

18C6,

in

with

aqueous

estimation

constants

ethers

crown

agreement

been

the

stability

from

ethers.

for

and

ethers

DB-6-hydroxy-19C6

polyether

by

cations

crown

constants

presence

crown

introduction

from

agents.[l561

(M = Ca-Bal

expanded

constants

H,O-CH,Cl,

B15C5,

metal

containing described[l551

satisfactory

extraction

earth

been

(M = Li-Cs)

M’

gives

alkaline

solvents has

extraction

complexation The

and

a more

ion are

systems stable

and

transport. more are

those

complex

43 with

the

cation.[1601

AC polarographic Na’

across

suggested

that

complex the

studies[l611

a H,O/C,H,NO, of

the

three

(in

the

formation

interface)

the

of

the

interface

most

kinetics

in

possible aqueous

the sites

for

phase,

probable

is

in

the

of

the

presence

transfer

of

DB18C6

of have

ionophore-ion

the

organic

interface

phase,

at

the

two

between

phases. The from

extraction aqueous

ethers

is

of

been

silica two

gels

resins

M’

(M = Li-Cs)

ether

using

matrices

(BlSC5,

water

showed

as

similar

Li‘

< Na’

*

Cs’

c Rb’

< K’

B18C6

Li’

< Na’

< Rb‘

< Cs’

c K’

321C7

Li’

*

< K’

but

the

resin

ability

to

resins,

the

been

x

be

both

pure

salts.

thiocyanate

cation

(Li-Cs)

water

[ 1641

conformation

using

At and

and the

is

at

interface

mirrors

distribution

of

The

precluded.

polyester-based be

considered

organic sequence

an

solvent;11651 of

extraction

K’

ion

replaced

as

the

the of

foam

for

The

SrZ+

<

Ba2+

at

as in

more

the

has

for by

when

factors

chloride,

interface on

the

alkali

in

highly

the

surface

metal

adjacent

extended pendant

polymer

for

M’

solution.[l641

picrates

between

presence of

governed

of

systems, by

the

water

DCH18C6

IDCH18C6Ml”X-

conventional is

solution

picrate.

the

of in

modified

air-water

is

affinity

extraction

lo3

spread

between

B18C6

DBlBC6

x

the

of

separation

aqueous

by

polymer

(M = Li-Cs)

constants

<

increased

1.5

B18C61

binding

pair

phase.[162]

anion:[1631

are

are

solutions

polyurethane as

the

and

aqueous

M’

modified

their

from

lo3

vinyl

that

(M = Mg-Bal

< Ca2+

in

to

binding

Hence,

M2+

sequences:

Using

for

x

interface

groups the

inferior

poly(4’-

cooperative

crown

B21C7)

mobile

MgZ+

(M = Na-Cs)

2.1

and

studied

;

sensitive

103,

cations

pendant

cs+

constants

x

the

ones.11621 M’

extremely

8.9

metal

been

of

*

were

based

extraction

iodide

Alkali

of

silica

104,

bromide,

has

to

< Hb+

columns

extraction

the

“1.5

of

the

shown

example,

based

metal

and

B16C6,

retention

B15C5

Na’

earth

containing

attention.[162-1641

of

crown

alkaline

matrices

increasing

on

and

of

and

3-D

separation

achieved

sets

alkali

onto

receiving

Chromatographic has

the

solution

ratio

by the of

and can

an

44 cation

to

1.4.3

Complexes

Coke1

crown

et

data ether

for

an

skeletal

made

between

cryptands provide

experimentally the

ions

of

framework

differing the

ligands,

guest

cation

electrode

and

K’

of

of

“cavity

nor the

have

structurally

analysed process

Coke1

et

(Scheme can

al.11681

intramolecular ethers

from

cations

in

have

ion e.s.r. the

be

they

direct

occur

on addition

studies

of

solutions

marked to

for

be

Na’.

cavity

formed

Using

when

Li’,

the (for

binding redox

for

Na’

cooperating

cation

one

electron

enhancement, couple

for

K,/K,

reduction

the is

macrocycle

binding

for

binding

transfer) For

sidearm

which

reduced

induced

transfer).

the

methods,

electrochemically reduction

K’,

since

Na’,

and

of

x

[(SlNal

Na’

selective lariat metal

e.s.r.

in

to

thought

size

to

the

x

have

lariat

ether 5.

K,/KI lo3

be

For = 2.4

(for

reduction

[(BlNal-

also

Scheme are

= 7.7

10Z could

are

al.11691

C-pivot

first

most

side-arm.11681 et

according

to

are

side-arm

closest

K-/K,

spectra

changes complexes

and

the

the

pivot alkali

the

enhancements

only

= 2.3

for

strongest

Coke1 the

but

also

reduced in

but

were

driven.

containing

changes

anion

voltammetric

enhanced

(401

electron

by

or

species

observed

cyclic

observed

radical

rigid

is

Na’

the and

which

nitrogen

electrochemically

Li’.

The

relatively

interaction

lo3

of

ion

for

complicated

evidence

redox-switched

of

of

enthalpy

in

presence

array using

determined11671

are as

pairing

N-(2-nitrobenzyllaza-15-crown-5;

group

obtained

N,N’-2-hydroxyethyl-,

described

gained

various

flexible

donor

four 4);

coincide

for

these

data,

been

concepts

Instead,

host’s

N.N’-2-methoxyethyl-4,13-diaza-18-crown-6,

complexation

and

size”

distances

thermodynamic

4 which

donor

Shannon For

N,N’-n-propyl-,

Scheme

chorands

data.

by

the

The

Comparisons

size”

organises

techniques,

complexes

in

complexes

defined

bi-bracchial

cations.

numbers.

Solution

and

illustrating

ion-to-donor

radius

xrd

cations.

listed

metal

for

coordination

41.[1661

selective

and “hole

metal

ionic

mono-

are

complexed

determined

of

crystal

potassium

drawings

explanations

effective

(Scheme

and

sodium

neither

satisfactory

with

range

of

structures

that

single

extensive

and

these

show

presented

complexes

or

connectivities

atoms,

Ethers have

charactersied

gives

Na‘

Lariat

complexes

structurally also

of

size.

a1.[166-1671

structural lariat

ether

two

induced

determined, not

the being

x

45

Scheme 4

46 observed.[l691

Kl (40)

M’

+

[ (&)Ml+

=

Ate

Ate

(-O-p0

c1

KZS

(s)-

+

M'

F!

Ate

0

KJ +

M'

[ (a)Ml-

*

(40) Scheme

By attaching Chang

an ionisable

et a1.[1701

selectivity

of the

by adjusting

ligand

ionisable

formation

to a crown

ligand

and Ca2'

logK,.,,_

< K'(2.781

ligand exhibited

completely

> Na'(4.02)

H

this mechan-

cations

in the sequence:

< Na'(2.75)

Ca2+(4.101

binding

membranes The and nigericin.

behaviour:

(41-H)-

(411,

through

of the complexed

increase

ether

to tune the

It is suggested ion transport

such as monensin

Ca2+(2.341

of the deprotonated

group

M' (M = Na,Kl

in pure methanol

form of the

(4i_) logK,,r.

Those

towards

5

it is possible

in biological

ionophores

constants

the neutral

that

the pH of the medium.

ism may be important with

pendant

have shown

0

\ /

OuO

(s)=-

-9 1 \

0

OCHzCOOH

> K'(3.721

reversed

for

47 The

selective

achieved

in

amphiphile

discrimination a mixed

(42)

of

bilayer

and

the

alkali

system

metal

cations

comprising

bis(12C41

the

derivative

double

(43).[1711

0-

has

(CH,),-NMe,

C,,Hz, -OC-(CH,),

been

chain The

+ Br-

a

(421

AI;) 0

C,zH,s

;+CH 2

\

0

/

C CH,

chiral

bilayer

dichroism

(421

due

Addition

of

suppresses

by

Na’

to

the

bilayers

the

Addition

of

N-pivot

the

fluorescence

547.

[ 1721

and

presence moiety

K’,

but

is

M’

(M = Na,Kl

and

endor

(46)

and an

(451

to

studies of

their

interaction but

not

that

Li’,

the

of

an

the

(441

the a

c.d.

factor

of

binding

of

ordering

a methanol

of

solution

enhancement

by

factors

perturbation

of

of of

of the

signalling

of

the

environments.

N-substituted with the

11731

of by

system

4.11691

remote

complexes

(46).

in

in

biological

of

bilayer

specific

Figure to

this

between in

in

quantitative in

the

results

(&1

chromophores.

mixed

increased

results

yield

suggested lead

not

(441

the

to

which

circular

the

suppression

attributed

(_431,

ethers

may

of in

or

to

similar

schematically

quantum

It

of

E.p.r. (451

Na’

lariat

fluorescence

is

shown

Na’

of

of

concentrations

moiety

as

of

intensity;

requires

crown

enhancement coupling

amounts

difference

the

presence

c.d.

marked

exciton

small

K’

This

shows

strong

very the

intensity -“lo=.

to

Na’

axacrown

Na’ ion

indicate and

the

ethers the nitroxyl

Figure

4.

Schematic

illustration

intensity

in an amphiphile-crown

of

the

suppression

/-\ 4El 4

(reproduced

by permission

from 3.

ether

of

c.d.

bilayer

Chem. Sot..

Chem.

Commun ., (1987)6173

r

1

0

cv 0

\/

N

\I

0

n

tn = 0,l) (441 (46) has shown that

Beer11741

the complexation

cations

(Na’,K’)

by

the

novel

(47)

modified

by

the

presence

is

(Ag’,Cu2+).

units

the absence

In

Schiff

of

of

base

of

transition

transition

alkali

metals,

N,S,

of

presence

of

chromophore,

no longer

which

Ag’,

available

the

1:l

for

K’;

prefers

tetrahedral

intramolecular instead

a 2:l

ether)

ligand

metals

(471 act independently to complex two Na’ (481 and cooperatively to complex one K’ ion giving

the

metal

bistcrown

the

two B15C5

ions

giving

(49).

coordination

sandwich complex

complex

In by the type

(501 similar

is to

49

50

that

formed

however,

by Na’

which

(501

prefers

the

complex

can occur

stoichiometry Using the

formation

of

novel

exhibit

the

giving

(501

lariat

ethers

selective

is

Na”,

unaltered

with

K’

sandwich the

at 2:1.[1741 have shown that

(521,

essentially

intramolecularly of

Cuz’,

by the NzSz

however,

et a1.[1751

molecules

complexation

of

intramolecular

with

Beer

cryptand

presence

coordination

I:1

(511:

techniques,

metallocene

bibracchial

planar

of

the complex

f.a.b.m.s.

In the

formed.

square

chromophore, type

is

sandwiched

to the exclusion

of

arms, Li’,

Na’

and Cs’.

pf = Fe,

(52: Alkali

metal

thiatolium

decarboxylation

substrate

1.4.4

Compared with been abstracted describe

the

of

bound to

Racrocvcfic

data

crystal

xrd

for

structural

separate

(equatoriallyl

interplanar

of

(Na...O

forming distance

of

Novel

Design

number of

Of these,

papers

five

characteristics

of

polyethers;1177-1831

the

have been completed

bipyramidal adjacent

others

340pm.

and (axially) staggered This

for

In the each Na

coordination

sphere

oxygen8 of the polyether

= 243.6.246.5pml;

a slightly of

have

the majority

I(~)Na,12’fC10,-),,[177J

= 245.5255.9pml

anions

aligned

the

by binding

centre.[l76]

analyses

in a pentagonal

are

of

and [(54tKl’SCN-.CRC1,.1178]

atom is

(Na...O

rate

calixarenes.[184-1851

structure

ring

a pendant

in ethanol

a reduced

subsection.

centrosymmetric located

the

acid

Polvethers

macrocyclic

I(~)Na,lZ’(C10,-1,11771

comprising

increase

and complexation

designed

18C6 with

catalytic

reviews,

this

synthesis

similar

to

pyruvic

as the

earlier for

traditionally Single

of

and acting

Complexes

report

(Na+,K’)

ion have been found

oxidative the

cations

Ruf

two oxygens the

of

two anthracene

sandwich

conformation

with

rings

an

differs

from

51

that

of

the

free

complexant

giving

sandwich

excimer

as

opposed

(53)

(54) to

monomer

fluorescence

[(~lK]‘SCN-.CHC1,[1781 2-fold

symmetry

oxygens

of

(axially)

two

270.2pm) anion

oxygens

remote

novel

a higher

intrinsic

and

the

crown

in

hence

the is

decomplexation complex

of

(M = Na.K,Csl

2-hydroxy-1,3-xylyl-18CS methods,

six and

(K...O

the

thiocyanate

=

increase

tridecalino-18C611801 for

K‘

the

fact

attack

the

by the

of

in

(581,

measured the

well

K’

with is

deeply

moieties

the of

the

1:l

(551, (571

in CH,OH by calorimetric

sequence:[1811

as

DCH18C6

decalin

2-methoxy-1,3-xylyl-lSC4

2-hydroxy-1,3-xylyl-15C4

as

cation

constants

(56). in

Na’, either

complex

by solvent

The stability with

over than

that

provided

from

K’

for of

the

cylinder

shielded

2-methoxy-1,3-xylyl-18C5 titration

to

process.[l801 M’

the 281.8pml

groups

ability

ascribed

lipophilic well

272.9,

phosphonate

ether,

The stability is

(equatoriallyl

arrangement:

selectivity

complexing

didecalino-18C6.

of

cation.

complexing

tridecalino-18C6 buried

separate

struture

on a crystallographic by

.O = 272.3,

(K..

bipyramidal

cylindrical

higher

lies

surrounded

ring from

from

K atom

is

polyether

exhibits or

and

in a hexagonal is

The

the

axis

the

In the

emissions.11791

and

52 (55)

logKn,_

Na’

(1.14)

< Cs’

(1.81)

< K’

(1.97)

(56)

logK,,

Na’

(2.30)

< Cs‘

(2.76)

< K-

(3.52)

(57-j

logK,,

Na’

10.8)

< K”

(58)

logK,,_

Na’

(2.25)

5 Cs’

DutchIl821

and

synthesised

the

JapaneseEl831 polytopic

4,5-dibromo-BlSC5, solvent

CH,Cl,)

report

that

relatively ions but

presumably are

towards this

CuCN

has

ions the

K’

dmf

for

forming

form

a monomeric

ions

bind

authors[l831 aggregation, may enable

two

also

by

the

of

refluxing

B15C5

The

for

M’

(Fe-Br,;

Dutch

group11821

(M = Na-Cs)

also

but

notef1821

a

that

K’

a complex

of

4~2 stoichiometry,

complex

of

4:l

15C5 a

comment

especially

independently by

20h.

They

(3.18)

(59)

bromination

Li’.

complexed

< K’

(1.30)

have

system

affinity

for

dimerisation

Li’

in

a high

affinity

satisfactorily

Japanese

that

low

induce that

with

(59)

by

< cs-

(2.62)

chemists

ligand

obtained

(1.26)

residues,

single

whereas

Li’

K+- induced to

high

tendency

of

aggregation be

used

ions

The

15C5 moiety.

on the

phthalocyanine

stoichiometry;

and as

a

(=I suggest

53 colourimetric The

reagent.

crystal

complexes

and

based

molecular

on

structures

calixarenes

of

have

two

been

alkali

[(6Q)Na.C,H,CH,J+[C,H5COO(AlMez~~OAlMe,l~,~1841 above

the

oxygens

plane

of

pyramidal

of

the

(44pm)

methoxy

geometry

aluminoxane

interacts

(Na...O

= 230pm1,

remotely

(Na...C

the

strongly

groups

being

anion

and

filled

by The

= 264pm).

of

7

apolar

cavity In the

The

is by

completely the by

R = OCH,CONEt,

calixarene.[I851

antibiotic

the

analyses Na

of

atom.

close

to

two

the

the

et

centre

and

paper)

on

et

the

ring

normal

two

extremely

-0

obtained

the

lies

resides of

the

et

K’

determined,

the

two

precise

had

location

giving

remote al.

in

[1861

the

results complex

of

the

Na atom

six 279pm) Now,

and

Pangborn

of

ring

(233.9-294.9:

Na...O

contacts

considered

cetion,

structural

the

average

contacts

for

location

located

(312.2,316.7pm).

the

preliminary

the

of

polyether

A

heteroatoms

Na...O

misidentified

have

(271.3-297.0;

asymmetric

corresponding

in

of

contacts

Pangborn have

a

structure

polycyclic

between

al.11881

.O contacts

six

may have

Jones

an

and

in

geometry.

cavity

molecular

monensin

difference

giving

(342.5,371.8pml.

K’

only

prefer

257pml

amide

calixarene

molecule

apolar

and

complex

complex

of

Na..

K’

Na..

al.11861

a1.[1881

adduct),[l861 the

remote

heteroatoms average

former

long

fairly

acid

The

Previously

anomalously

the

monocarboxylic

of

(dihydrate1.[187]

the

reinvestigated

(acetone that

time,

and

Iononhores

have

A204A

first

ether

the

methanol

(U-1

of

oxygens

antiprismatic

in

complex

the

of

R = OMe

Product

encapsu-

eight

.O = 270.8,274pm)

(601

Na’

the

the

calixarene.[l841

square

al.

the

in

the

(K..

et

of

atom

is

fragments

Natural

lies

four

square

a carbon

provided

the

its

atom the

~~~~K.CH,OHl*SCN-,~1851

lated

Pangborn

Na

with

molecule

K atom

1.4.5

In

toluene

located

But

metal

reported.1184,1851

it (only

confirming

that

being alluded this

in

Jones

et

reality, to

in

this

suggestion.

54 As

a

result

monensin

A

of

of

different complex

and

for

over

by

is

the

the

the

to

the to

of

the

of

the

al.11871

this

in

the

selectivity

is

complex

exhibited

accommodate geometry

the of

that

by

distorting

K’

ion.

the

the

Na’

of

monensin

A

the The

K atom

ionophore

of

markedly

corresponding

cost

encapsulating

K‘

discovered

complex

energetic

coordination

oxygens

et

in

ionophore

that due

ionophore

7-fold

seven

of

concluded

of

distorted

ionophore

that

K’

analysis

Pangborn

the

from

geometry

structural

(dihydrate),

conformation

Na’

their

is

provided

(K...O

= 265.0-

279.6pm).[1871 Lactonisation

of

carboxy-group

of

ionophores.

macrocyclic

ester.[1891

The

compared clear in

with

that

and

of

synthetic

recorded

in

CHCl,,and

obtained

the

n.m.r.

The

or

and

complexation

C21C,.

and

by

C222

dilactam

derivatives

covered some

in

this

molecular

data

octahedral are does

long, not

with

of

Li..

indicating enter

into

M+ and

C22,

Li

however,

either

interaction

of

the

C211,

M2’

C221

and

of

[196-1981

cations

and

structural

K’

by

the

C22212001

is

data

predominate,

included. [C22BLil’AlCl,-,

or

two zero

atom

isolated

trichloride

interactions the

weak the

of

Li’[1921

diverse

of

.O

of

C211,[193-1951

although

geometry;[l911

complexes

molecules.[l901

chloride-aluminium six

the

configurations

systems,

or

by

C21,

are

occurring

and

shows

existence

ionophores

result

chemical

similar

other

is

order.

CHCl,

n.m.r.

state

C22B,[1911

Na’

structures

n-butylpyridinium inclusive

and

can

naturally

in

it

Complexes

by

of

subsection;

thermodynamic

The

Li’

of

the the

anion

Related

of

by

Cs’[1991

of

5;

selectivity

with

adopt the

are

Figure

ionophores

ZSNa

solid

For

indicate

solvent

Na’[193-1951

the

tetranactin

fluctuation

Cryptates

derived

state.

signals

conformational

in

and

solid

been

Na’

ionomycinmethyl ligands

in

ion

of

those

1.4.6

the

the

have

monensin

with

in

of

ionophores

with

ions

changes

the

and

products

Comparison

with

Na’

natural

the

Li+-selective

these

of

Na’

==‘Na

for

complexes

shifts

of

of

two

monoacetate

modification

of

the

other

spectra

CH,OH.[1901

yielded

factors

small

large

esterification

monensin

relatively

n.m.r.

and have

selectivity

those

relatively ==Na

monensin

ionomycin

Li..

molten

(220.7-252.5pm) .N

contacts

interaction. coordination

from

the

salt,

is

in

a

near

(277.7,294.5pm) The

AlCl,-

polyhedron.[l911

anion

55

E f-in methyl

s* z*

.oCd’

4

esterit

1

ed+

U92'

-----iF 1.0

11.51.0

1.5

1.0

PO*

Figure

5.

Selectivity monensin,

factors ionomycin

by permission

(IogK ,,:j:interfering

ion)

and their

(reproduced

derivatives

from J Chem. Sot.,

for

Chem. Commun.,(1987)

932). The ionophore structure

of

also

exists

[CZlC&i]‘NCS-

in the

inclusive

in which

form

there

are

in the molecular three

(200.1.214.2,236.0pm)

and two Li..

.N interactions

in a highly

geometry.

The NCS- anion

coordinate Lincoln

irregular the Li

Li...O

(211.1,227.5pm) does

not

atom.

et al.f193-1951

have undertken

a comparative

study

of

56 the

complexation

of

constantstl931 methanol,

of

of

observed

for

by

and +, are

the

The

rate

relative

which

that

the

former

complex

than

the

latter.

The

attributed in

to

C21C,

(5)

the

supported

by

molecular

structures

shows

that

the

Na

the

all

exclusive

and

by

the

nitrogen it

.N

(Na..

of

and

the

of

K 1.6As1.6Te

C222,

and

when

complex

latter

cations

with

are

two are

mixtures

in

the

which

the

anion

which

(Na...O

the

and

adopt

the

[C21C,Nal+

(Na...N by

is

crystal

cation, =

= 257.6.275.9pml

of

the

= 235.8pml; four

(Na...N

in

oxygens =

by

the

nitrogen

in

ethylenediamine,

Ke S 5 and

and

Whereas

of

of

the

anion

the

are

three

gave,

analysis

was

(PC

yields

IC222Kl’

cations

of

all

of

= phthalocyanine1;[1981

undertaken

no details

are

the

in

five

[C222Kl+[tBuSladdition

in

those

related;[l971

after

crystals

and

distinct.11961

symmetry Reaction

[C222Kl+[FePcl

sulphur

with

[C222Kl+,Sez-

crystallographically

complexes

phthalocyanine

of

structural

of

en11961

unremarkable.

iron(II1

crystals

and

sites

conclusion

[C211Nal+SCN-

nitrogens

dissolved

~C222K1+zS,Z-.en.[1971

with

two

cryptand

[C222Kl+,[As,,Te13-.

former

the

of

oxygens

encapsulated

is

= 240.9pml.[1951

Reaction

the

of

is

and

(Na...N

to

stability

This

ligands,

three

labile

in

coordinating

study11951

the

and

solutions

much more

potential

Na atom:

the

nitrogens

cation,

247.8.249.2pml

of

two

.O = 228.9-266.2pml

(Na..

xrd

the

these

those

[C21C,Nal+

formation

(61.[193,1941

in

by

in

the

than

of

the

is

in

lower

difference

[C21C,Nal’SCN-

surrounded and

[C211Nal+

an

heteroatoms

coordinate

is

229.7-235.6pm)

the

of

of

of

C211

pyridine,

carbonate

IC211Nal’

number

with

results

the

form, atom

cryptand

reduced

compared

dmf,

instability for

of

indicate

and

stability

substantially

decomplexation

decomplexation

in

propylene

constants[l941

[CZlC,Nal+

The

C211.

determined

(CzHs14NC10

[C211Nal+. in

and

acetonitrile

0.05M

mirrored

C21Cs

[C21C,Nal+,

acetone,

presence

is

Na’

in

&H&l

pentane, although

reported

for

the

cation. The four

stability binary

propylene n.m.r.

constants solvent

of

systems,

carbonateldmso

constants

increased

abilities

as

given

In in

by

the

have

acetoneldmso,

and

techniques.11991

[C222Csl+

propylene the

donor

determined

solvents,

order

in

acetonitrileldmso, carbonateldmf

neat

inverse

Cutmann

been

of

number:

their

using

the

stability

solvating

lssCs

the

57 dmso < dmf < acetone In the

binary

< propylene the

mixtures,

monatonically

with of

The ability

carbonate

stability

< acetonitrile

constants

varied

composition.[l991

the dilactam

darivatives

of

C21, C22,

CZfl.

C221

and C222 (62 and alkaline earth metal -*- 631 to complex alkali cations has been compared with that of the unsubstituted ionophores

in methanol

potentiometric complexes

of

probably

and acetonitrife

methods;[2001 ths

owing

dilactam

using

th8 stability

ligands

are

lower

to a marked reduction

calorimetric

constants

of

by a factor

in the values

of

and the of

the

ca.

lo6

reaction

enthalpies.

oc”r\“70 NH

HN

1.4.7

n = 0,l

n = 0,l

(621

(63-j

Salts

of

Carboxvlic.

Thiocarboxvlic

and Dithiocarbamic

Acids The reduction chemistry

of

in the number of

alkali

and thiocarboxylic

and alkaline acids.

has been maintained in this

field,

molecular

structures

monothiocarboxylie interest again

in the

first

subsection Single completed

for

however,

first this is

of

notsd

in the

earth

of

of

of

acid

their

development crystal

salts

Cattow’s

dithiocarbamic

1985 review.

the

the

carboxylic

1985 review,

one interesting

and potassium

In view of

describing

salts

commented on in the

review;

lithium

papers

metal

the description

acids. chemistry

abstracted

and

of

continuing derivatives,

inclusion

in this

has been continued. crystal for

xrd

lithium

structural

have been

2-carbamoylphenoxyacetate

disodium

succinate,

hexahydrate

tartrate

(@).I2031

potassium

monopotassium

analyses (651,[2021

(641,[2011

monosodium di-meso-

dihydroxyacetate

cyclobutanedicarboxylate

successfully

(@).I2051

(67112041

and

The Li

atom in

58

1 Ho

- Li'

0

CH,C

1

2-

-0

2Na+,6Hz0

/O-

\ CCH&H,C b 0

$0

\ O(65)

NH, (64-j

7 0

HO //O \ o/CCH(OH)CH(OH)C\O

H

... . ..

l-

HO \

CHC

Na'

OH I

o, 'CCH(OH)CH(OH)C' \O

-

s C

K'

//O

I - K'

'OH

\ HO'

Oc/O-

ii 0

(67)

(64)[2011

is 4-fold

comprises

one oxygen

195.0pm)

and three

coordinate:

carboxyl

= 191.3-198.5pm).

coordinate,

located

of the Na atom

an anion

(Na.. .O = 238.0pm)

234.6-256.3pm);

and four

carboxyl

structure

K atoms;

of K(1)

comprises

carboxyl

oxygens

antiprismatic

The distorted

cubic

(Na...O

contains

two hydroxyl

geometry

octahedral

by one oxygen

molecules

coordination

from

(Na...O

=

of the

polyhedron

(Na...O

= 253.0.257.0pm)

= 246.8,260.7pm).

octahedral

The

coordination

(K...O = 274,275pm)

= 272-283pm) of K(2)

and

are 6- and

two crystallographically

the distorted

(K...O

(Li...O

in (65)[2021

in (66112031

on four hydroxyl

oxygens

of (6J)[2041

independent

Na atom

geometry =

anions

Na atoms

and five water

the distorted

(Li...O

from different

in (65) is generated

in (66) is based

tetrahedral

moiety

related

respectively.

geometry

Na atom

oxygens

The symmetry

the centrosymmetrically a-fold

its distorted

from the 2-carbamoyl

and four

and the distorted

is generated

by

four

sphere

sqaure

hydroxyl

59

fK.. .O = 274-302pm) and four carboxyl oxygens (K...O = 278-289pm). In Ctjs),[ZOSl the K atom is surrounded by seven oxygens (K...O = 260.2-301.0pm) from four different anions in a highly distorted geometry. The crystal and molecular structures of two monothiocarboxylates,

[PhCOSl-Li',tmeda (~112061

and

[SOCNHNHCOS12-2K+,2H~0 (70) and of one dithiocarboxylate, [S,CPhCSzIZ-2K'.2Hz0 (7J)I2081 have also been elucidated. The structure of 169)[206] is that of a centrosymmetric dimer with an a-membered ring composed of coplanar C, 0 and S atoms and tetrahedrally coordinated Li atoms fLi...O = 188.1, Li...S = 247.8, Li.. .N (quoted as typical of Li-tmeda complexes)) above and below this plane: ab initio optimisation calculations on

\

/

(

2,

N\ .HO N/L1\s

/\

\N/

S 'Li' 0'

'C'

'N 1 /\

(HCOSLI),, which is all planar, imply that displacement of the Li atoms in the complex occurs in order to reduce excessively large ring angles at oxygen and, most crucially, at Li in order to accommodate the tmeda molecule.IZ061

The two K atoms in (701

(2071 lie on a Z-fold axis; they are, however, crystallographically independent.

Each is surrounded by four oxygens (K(l)...0 =

272.9,273.8; K(Z)...0 = 272.7.278.5pm) and two sulphurs of different anions fKfl)...S = 319.9; K(Z)...S = 350.8pm) in a distorted 6-fold coordination geometry.

The two K atoms in

(7J)12081 are symmetry related: they are coordinated by five sulphurs (K...S = 322.4-353.ipm) from different anions and two water molecules (K...O = 274.8,276.8pm) in a distorted f-fold arrangement. Reaction of alkali metal formates with H202 yielded the formate peroxohydrates, HCOzNa.H,OZ and HCOZM,f.5Hz02 tH = K-Cs);[ZOQ] they are unstable at ambient temperature f293K) slowly losing

60 active

oxygen.

Alkali

metal

solvates, been

N,N’-diphenyl-N-formimidoyldithiocarbamate

[S,C-N(PhI-CH=N(Phll-M+,xL

produced

formamidine

the

the

K atom

and tga

anion

(K...O

bipyramid.

adduct is

related

of

is

potassium

by

moiety

the

in

the

been xrd

salti

have

sulphurs

of

a and

= 334.lpm1,

and

an

of

oxygen

a

of

solvent

trigonal

number

structurally

a

nitrogen

the

a distorted

coordination

dithiocarbamates

has

= 318.1,344.8pml

(K...S

form

smallest

have

mass

crystal

three .S

(K..

= 293.0pml

= 271.6pm)

and

behaviour

potassium

have

solvents They

n.m.r.

Single

the

solvent)

N,N’-diphenyl-

different

thermal

moiety

.N

in

of

hydroxide.

i.r.,

coordinated

(K..

This

CS, metal

their

L =

reaction

data.[2111

dithiocarboxylate

molecule

of

studied

all

the

thus

[2121

Cattow U.V.

et

a1.[2131

-visible,

1.4.8

Heterobimetallic

Sustained

perceived

growth

in

interest

in

heavier

alkali

and

the

this

those

in

on

into form

the

have

unremarkable

type

of

complex

(OC”Bu,),l-,[2141

one

metals

complex.

latter

type

species

such

included:

recent

can

be

reviews.

As

of

a

been

a K-Yb

two

sharp

rise

this former

[Li(tmeda),l’ Only

four

the

it

complex.[2351 types:

and

joined

in

For

abstracted;

distinct

cationic

the

as

has

are

for

complexes[214-2261

of

In

since

chemistries. are

of metals

despite

paper

discrete

two

Metals

complexes.[225.227-2341 one

the

(M = Rb,Csl.

chemistry

and

chemistry

fall

molecular

common cationic

this

using

techniques,

Alkali

alkali

review,

containing

which

the

containing

particular

metals

the

in

of

only

characterised,

containing

containing

period

structural

two

single

placed

interest

metals

and

spectroscopic

[S,C-N=C(CH,)-NH,]-M-

lithium

complexes the

a

of

sodium

the

These

mass

Complexes

reviews,

predominate

which

prepared

and

complexes

during

earlier

describes

also

n.m.r.

dithiocarbamates,

heterobimetallic

the

have

i.r.,

N-acetimidoyl

in

with

dithiocarboxylate

separate

by

u.v.-visible,

and

dioxane

monodentate

far.

dta

the

that

bidentate

a

by

from of

shown

(M = Na-Cs;

al.12101

alkali

techniques

elucidated studies

et

appropriate

characterised

spectroscopic

of

Cattow

(H-N(Phl-CH=N(Phll

containing been

by

by

those

anionic bridging

review,

ligands

emphasis

type

normally

or

~Li~tmeda~,l’~Mo~CO~~~~5-C9(CH,,,,I~,~21Sl

is contain

[18C6Kl’

examples

[Li(thf)4.,1+[Co(N(SiMe=)=}-

of

in

centres

which the

former

61 [Li(tmeda121+[Lu(“Bu)41_ Blue

12171

[2161

crystals

of

reaction

of

[CofN(SiMe~lzlZl

addition

of

LiN(SiMe,),

synthesised

as

reaction

of

was

obtained

by

is

unique the

thf

molecules

more

in

a

geometry

at

is

other,

the

more

containing

out

included

of single

pertinent

interatomic

Li-Ca

obtained

by

in but

thf. the

In;[2181 two

disordered

“fifth”

thf

position:

by

31pm towards

the

is

Li

the

complexes

include

Li-Ca,[2181

Li-MO.12221

and

Li-Lu[2261

complexes.

characterisation analysis;

structures,

and

molecule

axial

structural

distances

fifth

bipyramidal

Li-Cr,[2211

molecular

a

angles,

schematic including

collected

are

in

6.

The

Ca,

xrd

the

all

normal

with

statistically

[214,217-221,223-2261

crystal

of

crystallises

molecule.[214]

Li-Ni,[2171

cases,

complex

[2141

four

190-209pml

they

Li-V.12201

by

diethylether

heterobimetallic

synthesised;

Li-Co,[2141

representations

273K

been

thf

molecular

Li-Lu

usually

the an

plane

axial

of

the in

trigonal

that

occupies

trigonal

bound,

have

majority

Figure

the

Li-Ti,[2191

Li-W,[223-2251

has

of

near

indicates

solid

[Li(thf),.,l+

Li’

.O =

by

was

toluene

[Li(thf),.,l+,

= 256pm) The

and

LuCl,

thf,

(Li..

(Li...O

number

Li

of

Li’

of

cations,

In

to

atom

tightly

Li-In.12181

the

presence

active

pulled

complex

in

with

four

by followed

crystalline

sample

“BuLi

the

symmetry.

Li

A significant

In

the

molecule of

stereochemically atom

of Of

[Li(thfl,l+.

thf

centre

prepared

n-hexane

Li-Mo

yellow

A crystalline

coordinate

remote

about

The

thf.12141

interaction

since,

were in

[Mo(CO),H{SS-C,(CH,),)l

tmeda.[2151

tetrahedral

complex tBu,COH

sensitive

with

tmeda.12151

containing

as

in

[Na(tmedal,l’~Ni(C,H.,l~Hl-.

Li-Co with

a moisture

“BuLi

containing

the

and

the

lithium

(741

and

Li-In

treatment The latter

of

MCl,

former

has

has

distorted atoms

(75)

only

complexes[2181 (M = Ga,Inl two

one

with

bridging

bridging

tetrahedral

are

were Li(C(SiMe,l,l

Cl Cl

atoms

atom

coordination

completed

by

two

and

at

between

between

Li

Li

geometries

three

thf

and

and of

the

molecules,

respectively. The the

Li-Ti

lithiated

(Is-C,H,lTiCIJ heteronuclear

complex

(761

was

triaminosilane in

Et,0

bicycle

and

silicon

bridgeheads

the

roughly

trigonal

prepared

in

poor

yield

PhSi(NLi(SiHe,ll,

at

243K.[2191

[3111-heptane and planar

includes Li

It

reaction

contains

an

which

contains

entity a novel

coordination

by

with

Cl-Li-N is

unusual titanium

bridge;[2191

completed

by

an

of

62 ether

molecule.

Treatment lithium Li-V

complex

(77) Li

of

is

the

and

6.

in

(771.[2201

the

Schematic of

Li

atom

containing

the

is

coordinated

of

benzene

of

complexes

with tmeda

feature

of

representations

heterobimetallic

thf

thf

A novel

Y-coordination

V atoms;

Figure

the

in

the

333K

-_-/“\

to

molecular

both pseudo-

structures

containing

lithium.

thf

I 237

Cl

Cl

I Ca

Cl -

/\

[2181

In -Cl

I

C(SiMe,Phl,

C(SiHe,l,

tetrahedral

Li;

(~);[2181

80- 129”

tetrahedral 102-120” ‘average

194.9 - ’

z45.5 L / Li

.,r\

Cl -

tle,SiN

12191

value

Ti /

\

NSiMe3

N -‘Si’ I SiMe,

(761:

the

of

a distorted

243

\/

Et,0

gave

structure

LB7

Cl

Cl

at

molecule

thf

,e\

(74) :

u-benzene(dicyclopentadienylldivanadium

cyclopentadienide

‘Ph

trigonal

planar

Li

(771;[2201 planar

trigonal Li

Li;

63 Figure

6 continued. OH,

Hz0

Hz8

,

\

/

H*r;

,cr,-yLF \/

c=o

O-SC \

/ HOG

(78):[2211 “average

tetrahedral

Li;

104.8-115.6”

H

Li(2)-

H -

H-W--H

The

severely complete

Lit11

I

\

*

OH

value

H-W‘-

(=);[223:2241

OH,

N-N

/

distorted

W coordination

tetrahedral sphere

Li

is

omitted

clarity.

Ph thf

I -ii-thf

thf

Ph (fi);[2251

tetrahedral

Li;

105-115”

for

64

Figure

6 continued. C(C(CHs)3),

I thf *

192.2 thf

L

I 235.4 L -Cl

Li

OC(C(CH,),),

/

-co

‘OC(C(CH,)&

I thf

C(C(CH,) (=):[2141

tetrahedral 105-l

1

Li; (82)

13”

“average

33

; 12141

. . H=

(Li

(OLi 0

value

207pm) = 95.6”)

( ‘I=C,Hs)

/ \

( ‘IS-&H, Ph

1

Ph

Ni -) C

c,’ (83)

trigonal the

the with

Li-Cr

products an

OAE-Sephadex a

distorted

fashion,

C,H,

and

complex of

aqueous

hydrochloride

distorted

hedral

Li;

[2171

planar

parallel

The

(=);I2261

C

the

while C,H,-

(78)

solution

tetrahedral complex

-[Li-F-Cr-Fl-m

chains

NLiN

= 87.0”

sandwiched

between

on elution,

using

LiCl.

geometry moieties

K&O,. Li to

and the

when

atom two to

of

trans-[CrF,(py),l(NO,)

1,3-propanediamine-N.N’-diacetic

Each

along

is

crystalline

pH 3 by

column.[2211

Cr-containing

obtained of

of to

V atom

= 91.2”

rings.

was

reaction

adjusted

the

tetra-

PLiP

in

(78)

fluorines

two

water

a direction;12211

acid

separated is

on a

coordinated

from

different

molecules the

Li’

forming ion

in

65 seems

to

be

of

optimum

interacting

3-D

crystalline

products.

Wilkinson Li-W

network

et

complex

size

for

since

a1.[223,2241

(791

by

product

as

earlier12351

reaction

of

xrd

data

(R

permitted (79) atoms

that

are

Li

W,P,

to and

are

and

tetrahedral

in

(801, which

oxygen

thf

Addition

of of

CoCl,

with

quality however,

structure

which

atoms

the

months

better

The

Li

is

0.0359[23511,

in

the

complex

several

W(u,-HlLi,

“Bu,COH

and in

tetrahedral

of

the

by

W

normal

bridge;[223,2241

a

severely

distorted

of

secondly

with

(811

Li

the

in

(821

together

groups;t2141

there

interaction

other

by the with is,

a

the

is

atom

the

in

of

the

in

thf

a Li-Co

prepared

firstly in

an

by

with

thf.[2141

approximately

atom

and

three

thf

2-coordinate

moiety,

the

of

was

LiN(SiMe,l,

apparently

CoN(SiMe,l,

a methyl

to

(821

chlorine

is

thfl

in

of

thf.[2251

mixing

formation

surrounded

bridging

in

(in

complex

solution

however,

with

the

[Co(N(SiMe,l,l,l

atom

Li

in

CO and

of

by

‘Bu&OH

Li-Co

regular

equatorial

LiBEt,H

formed

and

resulted

an

4-membered

almost

reduction of

LiOC”Bu,,

an

of

by

equivalents

of

solution

on a planar

possesses

composed

n-hexane)

Et,0

based

atom

synthesised

The

fashion

molecules, bridging,

in

a

is

Li

two

(in

[2141

of

Whereas,

was

solution

“BuLi

(811.

treatment

.H

a

which the

using

of

solutions

Li..

to

atoms.

one

environment

molecules,

W,(COl,(lJ-PPh21Z

complex

by

of

This

al.

tetramer

4-coordinate

yielded

preparation

review;111

neighbouring

then

thus

complex

ring

slurry

two

et

opposed

hydrogen

Ba2’

alkyls.

1985

as

nor

strongly

geometry.

Li-W

three

the

K’

a

aluminopolyhydride

Green

the

of

the

lithium

centrosymmetric

bridges atoms

tetrahedral The

of a

connected

W(p,-HlLi the

of

the

by in

= 0.03151223.2241

location

is

reported

discussed

Na’,

reported

with

that

and

stabilisation

neither

have

[(Me,P),H,W(~-H),AlH(~-H)l= same

the

the

structure one

two

of of

alkoxide

(821 -

group

of

the

Li-Ni

complex

(=1.[2171

contact

between

the

a

close

alkoxide

anions. Reaction

between

tris(ethenelnickel(0)

trialkylborohydrides structure

yielded

exhibits

cation

and

in

[CC~‘-C,H,),Ni),C~-H,1-

the

one

pseudo-octahedral A puckered

Ni

an atom,

ion

the pair

one

ethene anion

coordination 4-membered

and

LuP=Li

lithium Its

[Li(pmdetall‘

molecule

and

the

giving

the

Li

atom

hydride

core

of

the

anion

a

geometry. ring

is

the

structure

66 of

(84) -

which

di-IJ-methyl methyl Li

was

obtained

complexes

Low

is

the

completed

temperature

7Li

ionic

Lil-

type

in

MoP,Li

and

(solvated)

which ring

the

tmeda

=lP

of

per

corresponding substitution

tetrahedral

of

geometry

studies12221

scheme

structure

the

the

the

of

6,

of

may be

assigned

on

Li’[cis-Mo(CO)s(W-PRR’)z-

anion

comprises

a

four-membered

(85).

(cO),Mo(PRR’H),

(CO),Mo(PRR’Li),

1

_ R’

R\p/ (cOl,Mo(

Li’

R.R’

= H,

alkyl,

and

sharp

rise

in

the

mainly

characterisation,

metallic

complexes

principally (USA) them

and they

to

have

published cases,

complexes. by

Cuastini

The

characterisation

only

et

schematic

representations

including

pertinent

interatomic

Single in

thf

attributed

Floriani’s

group

in

Parma

of

synthesis heterobi-

in

(Italy);

New

pertinent

paper

on a Na-Co single of

the

distances,

is

xrd

molecular are

and that

complex.

crystal

York

between

Na-Co.[229-2311

other

included

analysis;

Figure

be

a1.[2331

has

the

methods,

can

on Na-Fe,[227,2281

Boese

Klaui,

describing

structural

between

and

reported

papers

sodium,

collaboration

R’

6.

of

by

containing

Chiesi-Villa

Na-CUE2321

number

-

>Li yp\ R

aryl

Scheme

The

the

ligand.

n.m.r.

as of

core

system

of

stepwise

approximately the

prepared

(CO),Mo(PRR’Li),, an

by

reaction

HPPh 2 via

with

ligands;[226]

atom

by

In

all

structural

structures,

collected

in

7. electron yields

([Fe(acacen)lzONal,

the

reduction

of

([Fe(acacen)lnO)

centrosymmetric (86)

in

which

Na-Fe the

with

sodium

metal

complex ten

oxygen

atoms

from

the

67 two

{[Fe(acacen)laOI

units

for the two symmetry crystallises atom

with

coordination

Fe,Co,Ni:

Figure

7.

tmtaa

provide

related

three

6-fold

coordination

thf molecules, Similar

sphere.

polyhedra

Although

Na atoms.[2271

none are reduction

the complex

involved

in the Na

of M(tmtaa)

= dibenzotetramethyltetra-azaIl4lannulene

Schematic

representations

of heterobimetallic

of the molecular

complexes

containing

0

OG

N

N

Me

0

Me \

\ 'Fe' '\

structures sodium.

N

-0

Of---

---

(M = dianion)

/ c-o-

-0-c

I 'N

\

HC

1 N

CH

/

\ N=C

C-N I

Me'

I

\

Me

Hz& -CH, acacen

(&I;[2271

octahedral

Na : Na...O

= 230.8-257.7pm

thf thf,I jthf

thf thf, 1 /thf

Ph

Ph

thf'i 'thf thf

(8J);[2281

(=);I2291

Na...O

= 233.4-239.1pm

Na..

Na...N

= 277.5.280.1pm

Na...N

.O = 231.2-234.1pm = 275.7.276.6pm

68 Figure 7 continued

N\

HN

I ( /co\o \/ thf- Na-thf o

/\ O-Co-N

N-Co-O

(9o):r2301

(~I;[2311

Na.. .O(salen) = 239.3-256.3pm

Na(l).. .O(salen)

Na.. .O(thf)

Na(l).. .O(salendpk) = 228,230,

= 248.6.252.9pm

= 227,240pm 269pm = 223,234pm

Na(21.. .O(salen)

Na(21.. .O(ealendpk) = 229,231pm

0-N-N*

0

0

:

A

/1-

N \

N

0:

0

N=CH salen -O-i Ph&

r"CPh, salendpk

69

Figure 7 continued

(EtO),P -0

Only one of the anionic oxygen tripod ligands. [(ls-CsH,)Co(OP(OEt),),l-, is shown in full. (92);[2331

Na...O(bridging)

= 234pm )

Na..

.O(axial) = 228pm Itmean values) Na.. .O(equatorial) = 236pm 1 Na...Na = 327.7,329.0,343.1pm

0 -N-

N-

acacen

(=);[2321

Na...O = 236-255pm

0

70 gives of

the

the

complexes

Na-Fe

associated in

the

complex with

Nq

and

by

three

thf

280.lpm1,

the

anion.

of

The

are

in

[Co(tpp)l-

[Na(thf),l+ from which

reportedL2361 prepared

by

using

Reaction with

of

the

the

parent in

bidentate

equatorial

ratio

affords

which

third

a

two

hexadentate

Na

of

the

of Na-Co

atom

is is

bridges equatorial

two

Demetallation

the

for

the

the

recently

Co atom.

was

the

case

Na atoms,

Na

atom

complicated two the

of

also

[Co(tppll,

metal

complex act

which

completes

in

to

1:l

molar

a

complex

from

the

two

each

(=)[2311 moieties

surrounded

the

its

trans

[Co(salenll

of

as

by addition

imino

to

a of

two

(>C=N-)

ligand.

(921

has

been

a trimeric

crystallised

aggregate

bicapped to

by the

while the

ICu(acacen11

two

others

triangle.12331

are

a

donor

ligands; located

produced

([Cu(acacenlSNal’[Cu(SPh),l-.[2321

triangle

molecules.

oxygen

tripod

the

PhSNa

which

water

Na, by

from

in

three

anionic

of

Na-Co

located

is

one

(891

units

Na-Co

intact

resulting

salen

the

diphenylketene

coordinated

positions

gives

the

across

forms

dithiocuprate(I1

276.6pml.

[Co(salenlNa(thf),

molecules

asymmetrically

of

in

for

[(95-C,H,)Co(OP(OEt),),1-

one

distances

(275.7,

with

thf

ligand

also

extended

[Co(salenll

with

more

complex It

and

separated

second

molecules

atoms Na

(89)

where

acetone.12331 of

of

(salendpkl

A fourth

dianionl

ligand

complex

two

unit

functionalities

Each

with

bridge

diphenylketene

the

complex

coordination

identical

Na atoms

cobalt(I1)

interaction

between

[Na(thf),l’2[Fe(tpp)lz-,

ligands

Treatment

other.

(277.5.

related

somewhat

[Co(salenll

two

sphere

pair

is

ligand

distances ion

Na...Co

reduction,

atom

macrocyclic

Na...N

occur

isomorphous

bifunctional

which

coordination

is

Na

located

[Fe(tmtaa)l-

porphyrin

planar

is

thf.12291

complex

(~1[2301

in

in

the

the

a contact the

the

at

the

electron

metal

long

must in

whilst of

= tetraphenylporphyrin

complex,

single

sodium

of

which

Na-Fe

plane atoms

crystallographically

square

complex,

atom

of

located

atoms

provide

latter

two

are

nitrogen

also

The

the

cations

the

be

Fe

and

ions (tpp

which

to

the

interaction

[Na(thf),l+,[Co(tpp)l=(@)[2291

atoms

indicative

A similar and

metal

rather

cations

analysis

ligand;[2281

nitrogen

molecules.

12281

both

coordination the

fNa(thf),l’

[Na(thf),l+

shows

macrocyclic

planar two

however,

between

(87) -

the

square

coordinated

Structural

[M(tmtaa)Na(thf),l.[2281

the

atoms of

in

ion

these

axial

a

71 In

the

structure

chelate

the

coordination of

a

of

the

Na atom

cation

giving

latter

This

geometry.

coordination

cage

for

three

(931,

the

is

thought

to

provided

Na’

[Cu(acacen)ll

moieties

a pseudo-octahedral be

by

the

three

first

example

metal

complex

units.12321 The

molecular

dipotassium

structure

of

the

tetrakis

(diglyme)

adduct

bis(t-butyl[8lannulenelytterbate(III) The

complex.12341

Yb atom

is

(94)

sandwiched

between

of

is

the

two

parallel

Yb

(94-j [8]

annulene

the

other

rings

(Yb...C(averagel

sides

of

by

the

coordinated

the

rings

= 277pml.

(K..

three

oxygens

(K(l)..

.O = 275.1-305.6pm:

K(2)..

oxygen

of

the

other

diglyme

The

.C(averagel of

a

K atoms

= 308pm)

chelating

and

diglyme

.O = 276.2-302.0pml

molecule

(K(l)...0

cap

are

also

molecule

and

a

= 286.5pm;

single K(21...0

= 285.7pml.[2341

1.4.9

Lithium

Derivatives

A veritable occurred

explosion

during

abstracted

papers,

subsection. and

(from

nuclear

to

use

results

in

dodecameric, and

structural

dimeric

a

rich

further of

xrd

shell

diversity

systems

of

and to

monomeric

in

types aggregates moieties;

the

the

solid

(from

lithiated the

multi-

derivatives.

tendency

for

as

as

fully

varying

lithium possible

from

through the

sixty

this

describe

solution

orbitals

molecular

tetrameric

in

has

than

of

papers

novel

because

atomic

more

either or

of

data)

chemistry

with division

these

data)

predominates

valence

hexameric ring

lithium

review,

characterisation

crystal

spectroscopic

four

in

this

proportion

chemistry its

interest of

necessitating

single

n.m. r.

Structural

in

period

A high

synthesis state

the

trimeric

subsection

has

72 been

divided

metal

accordingly.

organonitrogen (95)

[N=C(NMe,),14 Produced

by

(excess)

(1

in

(Figure

8)

through

its

has

been

sequentially

O=P(NMe,), equiv.)

The

molecular

to

each

oxygen

of

to

has

the

of

by

of

Wade

et (2

“BuLi

a LiNa,N,

alkali

(1

a1.[2371 equiv.)

and

equiv.)

and

cubane-type

O=P(NMe,),

a Na atom.

a mixed

LiNa,[O=P(NMe,),l,-

HN=C(NHe,),

a mixture (95)

example

reported

adding

hexane,

with

first cluster,

ligands

Although

“BuNa

structure

terminally the

Li

attached

atom

does

not

(bl

Figure

8.

The

molecular

structure

IN=C(Ntle,),l, (in

1)

from

have

a

a methyl

1.4.9.1

Hexamers largest

described

so

Chem.

which

three

far

each leans

Li...H

and

is

by

tetramer

[(tBuCxCLi)4(thf),l of

the

selected “1

(b)

Chem.

of

LiNa,[O=P(NMe,),l,-

the

interatomic (reproduced

Commun.,

adjacent

perceptibly

distances by

permission

(1986)1740).

guanidino

towards

the

Li

groups

has

atom

interactions.12371

Higher

the

reported

structure

(in

Sot.,

structurally

Weiss,

with

angles

moiety,

group

suggesting

The

J.

terminal

(a)

and

of

Oligomers characterised

dodecamer

Schleyer

dodecamer

et

aggregate

[(*BuCxCLi),,(thf),l

a1.[2381

(97) (96)

organolithium

by (Figure

to thf

form

(96) from

cleavage. 9a)

can

the Since

be

envisaged

the to

73

(al

Figure

lb)

Crystal

9.

(b)

structure

of

(a)

[(tBuCxCLillzfthfl,

[(‘BuCxCLi)s(thfl,l.

dodecamer

and

the

tetramer

perpendicular

to

by

from

permission

the

plane

The

centres

lie

on

of

Angew.

and of

Z-fold

Int.

the

axes

projection

Chem.,

both

(reproduced Ed.

Engl.,

26(1987)5871.

result

from

tetramer

linear

(971

donors

at

a

dimeric

(Figure

each

represent

coupling

ring

Wade

et

principle

= R = Me,N solid

state

of

electron to

be

Li, which

The

stacking

by

to

principle.

the

stacking

together of

its

of

the

into

All

. six

been

the

structures

four

electron

two

slightly

in

a

pseudo-three

(R’

fold

of

axis

Snaith,

the R = ‘Bu

have

or

remarkably

Li,

imino

puckered

of

thf

folded

structures

staggered

by

the

by

= Ph,

(isoscelesl

hexameric

which

proposed

slightly

The

Li d Nb core

to

compounds

on

smaller three

terminated

the

aggregates

has

based

of

aggregates

according

(RR’C-NLil,

by

bonds.

projection

perpendicular

“Bul

bridged

brought

(RR’C=NLils 71.

are

for

structures

cores,

deficient

formed

account clusters

or

these

stacked

ring-stacking

chair-shaped faces

is

units

being

that

principle

1,2,3...1.[2381

to

cubane-like

aggregation

suggested

=

iminolithium

R’

similar

(n

three

the

is

[(‘BuCsCl,Li,l

a1.[239-2411

hexameric Me,N:

it

structural

[(*BuCsCIZLizll, A similar

9b),

end,

novel

of

ligands

triangular through

are

thought

trimeric

rings

conformation

(scheme

[Me,N(PhlC=NLil, (981

clearly

shows

the

74

Scheme 7

(31 Interatomic

Similar

folded

structures

of

(-);I2431

as for

structure Li

merit

Li,

cores

the

of

(1001 being

hexameric

of

satisfied

by the Lia

restricted

trigonal

space

antiprism

group;

by silicons, (ml12451

geometry

is

of

centered

six

Li,

faces

the

overall

a laddered

are

N . . *N

= 317.2-318.7

Li...Li

= 247.2-240.7

in the hexameric

and t*BuC(=CH,)OLil, clusters

the electronic the

enolate

the

however, of

on the i

and

is

into

is

dictated

based

symmetry si,tes

by nitrogens,

of

on an the Pi

the other

symmetry approaching

zrn (D,,)).

structure

of

consisting

the

the R

do not fall It

of

The hexa-

(=1[2441

trianion.

bridged

with

anion.

1~1[2441

structure

neither

structure

by an interaction of

(~1,[2451

The molecular

pattern.

= 196.1-208.1

found

[PhSi{N(CEu1Li131z

[HzC(CH,l,NLils(pmdeta), this

Li...N

iminolithium

figand,

the CH,=C< fragment

structures

are

(=1[2421

has an exocyclic

atom of

system

chair

IMe,SiCH,Lil,

distances/pm

That

two attached

two of

75 LizNz

rings

units

complexed

Cryoscopic solutions

Li-N

so

7Li

n.m.r.

spectroscopic

(1021

imply

that lengths

by

four

pmdeta

and of

suggesting ladder

(alternatively

similar should

that

the

compounds be

rungs)

preventing

with

two

terminal

further

association.

studies

of

ladder

framework

[RR’NLi,x

arene can

donor],

LiN

be

but

extended

of

various

preparable.

Interatomic

Me&3 i

distances/pm.

Liflf...N

=

193-204

Li(21...N

= 201-212

Li(31...N

=

197-221

SiMe,

\/

thf-Li

P /\ Me&5 i

Interatomic

SiMe,

distances/pm

Li(ll...P

= 244-264

Li(2)...P

= 248,255

Li(21...0

=

189

76 1.4.9.2

Tetramers

The tetrameric (1031,

of

decomposition

the dimer

product

and Holderich,[246]

has been

a ladder

framework

attached

LizP,

similar

to that

(alternatively

molecules

complexing

the terminal

extension

of

atoms are

coordinated

the

two

internal

Cubane state

type

latter

on a Li,C4 Li

(Li...C

224.0-227.6pm1

occurs

case,

the

occupied

type

centre

of

Li,O,

the

coordination (Li..

.N

carbon

through

coordinated

to the

4-membered

0-S-C-Li

the

central

Li,O,

A somewhat tetramer, because

the molecular two pairs (Li..

NMe, group

of

in the

the carbon

solid

Li

atoms,

thereby

and 0-S-N-Li

the Li

atom is

206.7pml.

A

lies

anions

are

forming

rings

at

the penta-

and nitrogen

sulphonimidoyl

four

=

atom attains

.C = 243.0pml

thf the

in this

of

= 206.2,

of

(Li...C

(~);I2481

each Li

(Li..

the

core

based

with

geometry

= 193.4-240.8pml

separate

atoms of

= 259-278pml

position

(~);I2491

atoms of

anions.

The

anchimerically

a chain

alternatingly

of

eight

annelated

to

cube.[2491 Li 4N4 core geometry

structure

of

faces

occurs

(1061

being

.N = 200.3,203.6pmf,

in the structure

(=);I2441

restricted

LiJ

Li

while

anions.

found

Li,C,

of

(Li...N

iLi..,O

of

irregular

the

similar

A

IMe,Sif(“BulNLil,l, of

two terminal

coordination

coordination

skelteton

and nitrogen

Li...Li

in the structure

structure

211.3pml

=

thf

(=1,[2381

tetrahedral

fourth

by a pendant

cubane

two

with

molecule,

by three

have been

= 217-229pm; the

= 192,199pml.

however,

comprises

preventing

the

and one thf

[(“BuC%Lil,(thfl,l

completing

atom (Li...O

to adopt

rungs).

atoms thus

surrounded

by Fritz

a1.[2471

It

Li-P

Hence,

structures

prepared

(1041 12481 and [(Me,Si)CH(S(0)(NSiMe,)Ph)Lila -* of (9J112381 is shown in Figure 9b, it is

That core

molecules

atoms are

of

IMe,NCH,CH&H,Lil, (1051. [2491

Li

et

(1021.

four

structure.

tetrameric

structures

of

by two anions

Li

first

shown by Lappert

rings the

[{fMe3Si),PLi}4(thf)21

i((MeJSi)2PLi},(thf)4f

of

distortion

the dianion.

is based

linked

giving

the

on a Lie

by the

approximate

of

the

arises

In reality, bisphenoid,

two N-Si-N TPm(D,,l

the

bridges symmetry to

the molecule. The dilithium prepared

salt

by reduction

lithium

powder

dimeric

sandwich

of of

in toiuene

the the

1,3-diboratacyclobutadiene 1,3-dihydro-1,3-diborete

(scheme

compound with

81,

a Li,

crystallises layer

(Figure

(1071, (1081 with as a novel lOt.[ZSOl

77

R’ R-B

A

2Li’

ZL.!

B-R

e--i

_i)

R-B

B-R

c6”,jc”I R’

R’ (107)

(1081 8;

Scheme

R = -C(CH,l,;

R’

= -Si(CH,),

(b)

(al

Figure

10.

Projections salt of

of the

of

the

dimeric

structure

a diboratacyclobutadiene pseudo-C,

axis

(b)

Interatomic

“sandwich

axis”.

over

halves

both

and

(a)

of

the

dimerl

in the

of

the

dilithium

in

the

direction

direction

distances Li(l)...Li(31

Li(21..

.Li(3)

= 247,

Li(l1..

.C(21

= 227.6,

Li(ll...C(41

= 234.6,

= 225.4,

Li(3)...C(21

= 209.9,

Li(3)...B(ll

= 223.7,

Li(2)...C(41

Li(l)...Li(21

Li(31..

.C(41

= 219.6,

Li(31..

.B(3)

= 245.5pm

Angew.

Chem.,

Int.

Ed.

the

(averaged = 233,

= 313,

(reproduced Engl.,

of

by permission

25(1986)1111).

from

78

1.4.9.3

Trimers

The

only

lithium

structurally

derivative

with

characterised (~I,[2511

[((Me,Si),CH),Lil,

a trimeric

within

((Me,Si),CH)aAsC1

in Et,0

at

boat

conformation

an average

geometry

period

prepared

with

with

the

of

by

to

this

reaction

of

298K.

The Li,As,

Li...As

interatomic

be

review

is

lithium

ring

has

a

distance

of

260(4)pm. 1.4.9.4

Dimers

The

synthesis

complexes

been

direct

lithiation

Single

crystal

are

based

a large

of

has

using xrd

distorted

Li

a metallating

trigonal solvent

(1101,

(111))

(e.g.,

(112) ).

planar

molecules or

agent

such

has

shown

analysis

coordination typically

thf, with

(*Bu),As

\

Et,0

As

Ph’

‘Me

/

extended or

by tmeda

functional

structures

majority

to

either

inclusion

of

(e.g.

groups examplified

by

n/

‘-0

\

\

the

“Bu 1

/\

/

“BuLi.

that

tetrahedral

bonded

complexes

as

was

and oxygen[262-2651) being

distorted

intramolecularly Those

method

nitrogen,[253-2581

geometry

or

lithium-containing preparative

arsenic[260,2611

atom

either

dimeric

favoured

(X = carbon,12521

on Li2Xz

the

of

the

structural

phosphorus,[247,259,2741 rings,

number

described;

3

/L1 As \ As(~Bu), tBu’

\

(112)

(110) (111) (110.111,1121 structural based

on Li,X,

(Jx),[2661 and

are

listed

in Table Three

details. rings

11 together

slightly

are those

more

in the centrosymmetric

dimeric

of

and to two benzene

and to the ether

oxygen

(Li...O

structures

(m)[2561 The Li atom

(m).[2631

structure

to the two nitrogens

200.0,207.6pm)

pertinent

of [(H,C=C(tBu)N(Ph)Li~,(EtzO)zl

[(Me,N.N.C(CH,),C.CH(OMe)OLi~z(thf),l

[~PhzPCH,C(tBu)zOLi~z~~~Bu),C=O~l

coordinated

with

complicated

of (-I[2661

the Li,N,

carbons

= 193.7pm).

ring

(Li...C

is

(Li...N

=

= 243.7,266.2pm)

The two Li atoms

in

79

Table

11.

Structural complexes

details based

Li,X,

Molecule

r(Li..X)

ring Solvated

Lithium

for

diverse

on Li,X,

pm.

dimeric

lithium

rings. Li

Exocycl

C.N

ligand(Y)

ic

r(Li.

.Y)

Ref

pm.

Derivatives:

[(PhN(CH)sCLi),(tmeda)zl Li,C,

219.1,218.4

4

tmeda

219.9,230.4

252

Li,N,

202.5.202.5

3

thf

188.2

253

3

thf

192.6tav)

254

[((MeJSi),NLi),(thf),l [(Me,Si.NH.SiNe2.NH.SiMe2.NLi),(thf)z~” Li,N,

203.5tav)

[(Me,Si.N(SiMe,).SiMe,.NH.SiMe,.NLi)zfthf)z~ Li2N2

201.7.206.1

3

thf

191.2

255

Li,N,

201.2,207.8

3

(‘Prl,NH

212.4

256

208.2,208.2

4

tmeda

229.6,229.6

257

204(av)

4

tmeda

205(av)

258

[(Ph2NLi),((‘Pr),NH),1 [(Ph(Me)NLi)Z(tmeda)zl Li,N, [(PhCH:C:NLi),(tmeda),1 Li,N,

[~(2.4,6-Me,C,HZ)2PLi),(Et,0),l” Li,P,

249.8tav)

3

Et,0

190.8(avl

259

Li,P,

261 av)

4

tmeda

213.8(av)

274

Li2Pz

262 262

4

thf

192,203

247

Li,As,

258 258

3

thf

189

260

LizAs,

270.8,275.7

4

Et,0

197.4,199.7

261

181 (av)

3

thf

206(av)

262

4

tmeda

213(av)

264

[(Ph,PLilp(tmeda)Z1’ [((Me,Si),PLi),(thf), [((‘Bu),As(“Bu)AsLi),

thf

21

[(Ph2AsLiIz(EtzO)~l [~~SiMe,),C.SiMez.OLi),(thf)zl Ll*Oz

~~Ph(Me)C:S(Ph)OLi~,(tmeda~zl Li,O,

192fav)

80 Table

11 continued:

Intramolecularly

coordinated

Lithium

Derivatives:

[Me,PCH,C(tBulzOLilz LizOz

181,176

3

-PMe,

250

263

Li,O,

178.7,179.7

3

-PPh,

265.1

263

196,208

4

-P(OlPhz

189,192

265

[Ph,PCH&(tBulzOLi12

[(Ph,P(O)CH,CH,),NLi1,2’ LizO,

* Two

crystallographically average

structure;

the

structure

are

chemically

oxygens

of

of

the

hydrazone

by

the

two

thf

molecules

the

Li

the

two

phosphorus

(1141

Li,O,

are

ring

of

(Li...O are

the

oxygens atoms

of

the the

Li,O,

Li,O,

coordinated

191.9pml

present

in

the

ring

Lit21

(Li...O The

=

ring

derivitised

the two

is

192.7pml

.O =

alkoxide

is

two nitrogens

and

two

polyhedra

of

arangement

coordinated

180,187pml anion

axis,

encapsulated

A similar

Lit11

(Li..

the

coordination

tetrahedra.

I=);[2631

symmetry by

and

= 202.3pml;

192.9pml.

of

are

on a P-fold

is

.O =

flattened

structure of

Lit11

(Li...N

=

both

located

(Li..

the

dimers

quoted.

although

residue

oxygens

atoms

in

data

distinct;12561

the

of

pertains

independent

and

(Li...P

by the =

two

81 (‘Bu), Ph,P

f-5 \

/O\ Li(l)

Li(2)-OmC(*Bu),

I\/

259,263pm)

in a distorted

tetrahedral

by the

oxygens

Li,O,

the

two

oxygen

planar

of

are

coordinated

they

and also

group

of

oxygen

ring

(Li...O

ketone

(Li...O

atoms

nitrogen

210pm).[2671

pseudo-tetrameric

is

surrounded

= 180,183pm) = 197pm)

of

remote

anion

The other of

Li

atoms the of

contact

atoms

anions the

of

atoms

(Li(2)...C

two

separate

atoms

atoms

and carbon

a relatively

bridging

complex

The two Li

nitrogen

nitrogen

have the

the

ring.[2671 by the

the

303,334pm). two

of

on a Li,X,

anions

the

solvating

Lit21

and by

in a trigonal

geometry.

The structure based

of

the

array;

ligand

/

N-

distanceslpm (116)

bridging the

with

other the

= 324,337; are

is

also

Li2N2

anions:

methylene =

by two

= 190pm)

(Li...N(average)

core

sulphoximide two

Li(3)...C

encapsulated

(Li...O(average)

tmeda

(116) in the

=

and the

a2 Unusual

bridges

[LiBH,.tmedal,

occur

in the dimeric

(=).I2681

structures

[(Me,Si)zNSi(Mel(F)O(CMe,)zN(Li).Si(CHMez~zF~~ [~CH,=CH.CH.S(Ph)O~Lil~(diglyme),l [(MeO.SiMe,),CLil, (=)[268] atoms:

each

lJ,-H atom

pz, n3-BH4

apiece

coordination

both

doubly

group

(m)[2711

sphere

and triply

bonds

and through

(m),[2691 (119),[2701

and

The centrosymmetric

(=).[2721

contains

of

[fEtOLil,(PhCH,NO,),l~

to two Li atoms

one r,-H atom.

is completed

dimer

bridging

hydrogen

through

one

The Li

of the tmeda

by the nitrogens

molecule.

Et0

/

'0 I \

I

(117)

(G)

MezHC,

,CHMe, Si

(Me,Si),N

/%I.:,

O\

/I(.

(CMe,),

)

-

-&ri\

"(

/O

Si-N

F -Si \

*YF

(Me,c/,2

\ N(SiMes),

A Me,HC

CHMe,

83 Me I 0 -Si

Me, I

I

c

0

CO

I

Ph

Ph

\

thf thf \ Lit;)

P

Li (2) (

thf

,thf

\

\

/

/ P

0

thf

thf $iCl) thf

ip Ph

\

/ Li (2) 1

\

\ thf

p\ Ph

(122) distances/pm

M.O.

calculations

adducts

with

stabilities

one

Li

using

geometries

for in

its

O-N-O

second

rings,

comprise

bridged

The

are

and

the

The

bridges

polyhedron

and

its

their

Li,HB

by a

whilst 3-

and

4-centre

by

in

the

Li

the

free

(Li...O

moieties

anions. of

atom

The is

give

a

tetrahedral oxygen of

of

the

annelated

=

centrosymmetric

-N--Si(CHMez)ZF

anions,

to

framework

molecule the

nitronate oxygen

distorted

ribbon-like

ethanol

two

single

completed a

[(Me,Si),NSi(F)OSiN-Si(CHMe,),FIcoordination

[LiBH41Z how

contacts, and

other

ring.

giving

the

Li...H LiHB

are the

atoms

anion

on show

compounds.

moiety,

Li

191.9-197.9pm). (m)[2701

such

of of

(-I[2691

the

nitronate

6-membered

number

6-membered of

leve1[2681

geometries

inadequacies

atoms

Li-0-N-0-Li-0

6-31C

1=-BH, the

the

structures

The

the

and

reflect

illustrating bond

at

Q2-

structure of

the

trigonal

completed

by

planar the

other

of

84 fluorine

Hence,

atom.

Li-F-Si-0-Si-N 8-membered

structure

Li-0-S-0-Li-O-S-O the

which

are

The Each has

completed

the

C,,

point two

giving

group to

two

rings

from The it

cleavage

exists

as

power

of

a P-acyl

of

the

are

the

two

types

P,Li=

Monomers crystal

monomeric

(or

dimer.

own -0Me

groups

4-membered

in the

at

the Li

which ring,

other

Li

There

is

atom

atom

Li

end

of

atoms giving

the is

in which

with

atom

diphosphide

which

the

or

atoms

significant average).

intramolecularly

(PLi(2)P of

unusua1;[273]

P and Li

(257.3pm

bridge

lithium resulting

chain.[2731

very

no systematic distance

intermolecularly lie

out

the

the

8-membered

= 113.5”).

plane

defined

ring

the

by the

appearance

and Polymers data

polymeric)

have

such

of as

thf,

the

remainder,

of

the

Li

atom

diorgano-amides.12571

arsenides[2611

the

Li

E&O,

atom tmeda.

stability

the

pmdeta is

features 3-coordinate

19 are

anions

and

and

generated

by

ligand.

Several

and fall

are Li

into

collected

[(Ph(naphthyl)NLi).tmedal,

formally

for

The majority by both

by a polydentate

structural

The diorganoamide, each

and analysed

monoorganophosphide[2591

pertinent

; 12571

collected

derivatives.

phosphides[274,275

and a single

category;

been

lithium

for

encapsulation

dimers”

dimer ring

with

the (122)

interatomic

Li(l)

xrd

molecules

diacetamide;

each

derivative

by coordination

12.

molecules.

a cage dimer,

to

Li

of

chair.12731

Single

Wloose

of

system

an elongated

stabilised

.P

and,

the

remaining

Table

Li..

= 86.9-j,

respectively:

former

of

conformations.

gives

a centrosymmetric

in an 8-membered

lithium

the

in the

a planar

tetrahedral

bond

in

solvate

in boat

ethane

variation

1.4.9.5

its

of

diglyme

that

coordinated

sonication

alternate

of

the

alkane-l,n-diylbis(diphenylphosphine)

low

structure

(PLi(l)P

groups

from

of

of

a

cage.[2721 of

with

There

one

giving

the

geometries

molecules

has

atom,

6-membered distortion

Reaction thf

symmetry, own Li

in

bridging

essentially

(MeOSiMe,)&Li

two

case,

bipyramidal

oxygens

is

-0Me

coordination

by sulphonyl

three

remaining

considerable

in

its

occurs

in this

trigonal

(=)[2721

structure,

Li-F-Si-N-Li-F-Si-N

ring

(m);[2711

formed

by the

of

component

coordinated its

is

in the

and a single

8-membered of

distorted

structure of

and

ring

5-fold

exist

rings

A similar

ring.

centrosymmetric atoms,

3 rings

6-membered

the in

forms atom

interacts

85 intermolecularly

with

neighbouring

phenyl such

312,315pm), the

pairs

of

Li..

.P

Table

ortho

molecules

is

towards

are

cations

and one

Although

group.

association

diorganophosphides alternating

one

meta

weakly

emphasised each

bound

they

and anions

of

the

(Li...C

by the

=

displacement

other.12571

polymeric;[2751

[Li(thf),l+

CH unit

Three

consist

of

of

[R,Pl-

of

the

chains

held

of

together

by

interactions. 12.

Structural

details

organoamides, Compound

for

diverse

monomeric

organophosphides anion

and

lithium

organoarsenides.

Li

RZX-

C.N.

X

r(Li..X)/pm

Solvate

N

200

218,221,222

257

3

N

197

212,213

257

4

P

256.7

209.1,212.6,215.0

274

4

P

253.3

194.9-198.2

259

4

P

262.9.263.4

193.7.198.8

275

3

P

245.5,254.3

193.6

275

(1)

3

P

248.6,249.6

192.5

275

(2)

3

P

248.3.249.2

196.6

275

4

As

266.0

193.1-196.8

261

X

Molecule r(Li

Ref

. .X)/pm

[(Ph(naphthyllNLi).pmdeta 4 [{Ph(naphthyl)NLi).tmeda

[(Ph,PLil.pmdetal

[(2,4,6-Me,C,H,(H)PLi).(thf),l

[(Ph,PLi).(thf),lw

[((C,H,,),PLi).thflm

[fPh,PLi).Et,Olm’

[(Ph,AsLi).(thf),l

Two crystallographically asymmetric

unit.

independent

formula

units

exist

in

the

86

Minor

changes

variation. aryl to

in

An xrd

thiolates, chilled

shown

the

that

anion

an

(253K<3 toluene

solutions derivative

2-MeC,H4S-

Li-S Li

-(Li-S)-

derivative

rungs, atom

the

(1231,

is

sulphur

tetrahedrally varies

from

thiol

is C,H,S-

[PhSLi.(pyIzlm

while

ladder

three

9 9 :I

the

\

PY

core

(=),[277]

membered of

the

while

S

I S -

I / Li \

‘0

PY

(I

py

.S)/pm

b

r(Li..

245.9,251.3

206.3,208.5

(125)

245.4-250.8

204.5,206.8

[((“Bu),P),SnLi.thfl

and

PY

.N)/pm

(124)

structures

PY

:’

208.1,208.1,208.3

LiP,Sn

around

I S-

241.2

molecular

with the

coordination

(123)

Lip&,

the

polymer

Li-

/

Li-

r(Li..

Four

a polymer

Py\

PY,

-Li

has

structures

PY

I /

“BuLi

4.12761

(123)

the

is (124)

folded

coordinated

-S’

of

and pyridine,

derivative

in all

‘I \

lithium

solutions

a monomer

(125);

2 to

structural

crystalline

hexane

an infinite

[IPhCH,SLi).py]m

of

of of

the

chain

forms

remarkable

a series

by addition

the

infinite

C,H,CH,S-

induce

of

study12761

prepared

[(2-MeC,H,SLiI.(py)31 with

often

LiP,Pb of (=)[2781

rings

have

been

[(Ph,P),CHLi.tmedal and

found

as

07 [((tBu),PI,PbLi.thfl synthesised MeLi

by

in Et,0

The Lip&

(1281.12781 lithiation

of

containing

rings

in

(126),[2771

bis(diphenylphosphino)methane

tmeda,

exhibit

mean Li...P

with and Li...C

(“Bu),

I

\

Yhz

/

jp\

thf-Li,P,E-P(‘Bu),

N\ yp\

(/ N/L1\pOCH \

(%Bu),

;h,

(126) distances

of

geometry

of

molecule

(Li..

and

258.2 the

Li

251.5

172.2pm,

atom

is

obtained in

rings

thf

have

sphere

of

Two monomeric atoms

have

Li

is

containing

prepared

both

LiCl

centrosymmetric the

Li

atom

the.three

linear is

obtained

by

halogen

reaction

of

\

Li-cl

-Li

N<

0” -

of

tridentate

latter the

N-

Li

and The

to

parent

(=I[2791 (Li...Cl

pmdeta

molecular

ligand

aminofluorosilane

with

I

I

and

in a distorted (=),[280]

thf

a

in which = 217pm)

complex

thf-Li

former

toluene contains

cation

chlorine

thf

I

coordinated

pmdeta

centred

+ II

coord-

molecule.

(~I.[2801

by the

\I

N'

thf

[Li(thf),l’[Li(C(SiMe,),),l-,

the

The

I r -N -

of

planar

(=)[2791

chlorine

array.

trigonal by the

248.5/-

characterised;

encapsulated

nitrogens

tetrahedral

with The LiP,Sn/of

the

by addition

and

(127)

.P distances

completed

containing

structurally

tmeda

complexes,

[(“Bu),PLil

and SnlPb..

atom

tetrahedral

bidentate

“ate”

[(2,4,6-(Me,C),C,H,N.Si(‘Pr),FLi)fthf),l complex,

the

of

[f(pmdeta)Li),C11+[Li~C(SiMe,),),lionic

(128)

isostructural.

respectively:

the

complexes

been

The

are

mean Li...P

E = Pb

by the

by treatment

and 268.7/278.6pm,

ination

completed

solution,

(127)

respectively:

.N = 203.3,207.2pm).

(m),[2781

SnC1,/PbClz LiP,Pb

and

E = Sn

MeLi

CHMe, -

F -Si

I

-N

I CHMe,

(131) (130)

-C&.H,(CMe,),

in

88 thf , contains comprising thf

fluorine

the anion

of

Li

(Li...F

Five

organolithium

adduct

(132),[2811

(m),[2821

lithium, Li

to this

characterised:

(=),[2831

adduct

I=)[2841

tmeda adduct atom,

ether

that

Although

(132f[2811

of

in the polymeric above

predict

Li..

structure

the Li

represents

atom.

the

decker is

example

of

247.255.3pm1. nitrogens

216.4pm).[2841

the

for

in

bonded ab

to

lies initio

of

the

ring

carbons

simplified

the bidentate

of

(=I;[2831

of

theoretical

of

(=I.[2831

atoms

shifted

lie

atoms

tmeda molecule

C2

above

and

from the borons

= 226.3-236.8pm; the Li

the

it

crystallographic

The Li slightly

above

charge model

with

group

basis

and 214.lpm.

C-Li’N-Li’C-

(Li...C

a 3-21C

the ally1

209.3

structure

structure

The coordination of

of

214.1,

by (=).I2841

diboratabenzene

direction

group

(=)I2821

using

the predictions

sandwich

adopted

of

in the

and confirms undertaken

A triple

of

Theoretical

allyllithium

disposition

occurs

a beautiful

calculations symmetry

unsolvated

.C contacts

OS-bonding

communication

the

for

a symmetrical

atom with

the ally1

is asymmetrically

(133)

calculationsE2811

the

pmdeta

adduct

and bicycloI3.2.llocta-2,6-dienyl

(132)

below

have been

1,2-diboratabenzenelithium,

(=I.[2851

structure

symmetrically

Similar

section

allyllithium,

1,3-diphenylallyllithium,

adduct

the monomeric

set

sphere and three

2,6-bis(trimethylsilylmethyl~pyridinedilithium,

bis(tmeda)

almost

compounds pertinent

and structurally

bisttmeda)

Li

coordination = 182.2pm)

molecules.

synthesised

the

tetrahedral

an approximately

the

is

Li...B completed

1216.2,

= by

in

89

H,N

NH3 ‘Li’

/

c-_c

14\

Me,Si-t’-C

‘C

WN_C@

H

I\

\ \

C-SiMe,

1

1

I(

1

C-SiH, I I ,‘A \ 1/ \I/

,Li

H-N

In

the

an

almost

not

only

molecular

olefinic in

structure

central the

allylic

part

of

metal-ligand

geometry

position

is

(Li..

the

of below .C

bonding.

the

7-membered

(Li...C

The

by

the

Li

atom

ring,

= 219.4,244.0,251.5pm)

carbanion

achieved

(136).[2851

tmeda

Li

atom

occupies

such but

also

= 239.9,242.9pm)

7-fold

‘NH3

is

that the engaged

coordination

solvation.

NMe,

NHe,

(135) The

last

of

the

solvated

complexes

bis(diacetamidel(nitratollithium surrounded

by

molecules (Li...O

(Li..

five .O =

= 200.lpm1,

in

oxygens,

provided

198.7-206.8pml in

a

slightly

to

be

which by and

considered the

two

Li

atom

bidentate

a monodentate

distorted

trigonal

geometry.[2861 The 12871

monomeric and

cations

in

[N(CH,CH,OH),Lil-[2,4-(NOZ,,C,H,ol-

[N~CH,CH,P~O~Ph,~,Lil+~~~N~CH,CH,P~O~Ph,~~Li~~lz~-

is is diacetamide nitrate bipyramidal

anion

90 (138112651 _

(BPh414

encapsulated atom

is

by

contain

192.4pm)

by

a

In

the

trigonal

by

181-188pm) position in

with

was

complex

of

and

imine

structure

donors

pyramidal five

by

a

in

.N

atom

of

the

seven

molecule

more

remote

second

cation

1.4.9.4.1

described

which

trigonally =

of

incorporating

a very

=

(Li...O

the

characterisation

in

(Li...O

is

slightly

subsection

by

lithium

et

pyridine al.12881

independent

unusual

pentagonal-based

equatorial

and

a

only

Lewis

sites

heteroatoms

= 214.2-228.3pm)

methanol

a

been

macrocycle’s

Li(21..

at

Li

=

In

Li

structure

crystallographically is

molecule

tripodand

has

environment,

solvent

the

two atom

the

the

macrocycle

Li

of

227.1pm;

(139)

Each

of

[The the

water

the (Li...O

arrangement.

structural

contains

molecules.

the

nitrogen

in

and

a pentadentate

The

by

pivotal

considered

preparation

and

oxygens

= 257pml.

wholly

tripodand

however,

three

the

(Li...N

(1381 The

the

or

[N(CH2CH,0H)3Lil’[2871

bipyramidal

IN(CH,CHzPfO)Ph,),Lil’,[2651 coordinated

partially

tetradentate

= 220.6pml

Li...N in

atoms

tripodands.

coordinated

198.3-201.8;

Li

the

(Li(l)...O

are

occupied

(Li(ll...N axial

= 214.8-

site

= 204.1;

is

occupied

Li(2)...0

=

201.7pml.

A Japanese

group

electrolysis 0.1%

vs

complex

of saturated of

the

which

(Figure

Li’pc

-

staggered 1.3Pe

at

has

the

shown

that

dilithium calomel

molecules by

38.7”;

298K

to

contains of

S, its

l.Or,

of

electrode

phthalocycanine 11)

controlled

salt

in

CH,CN

radical,[2891 a unit

cell

symmetry,

stacked magnetic

150K,

but

upon

gives the

with

effective at

potential

phthalocyanaine

four

Li2+pcZ-

a lithium of

structure nearly

planar

metal-over-metal moment further

at

but

decreased cooling

from it

91 increased

Figure

to approach

11.

the

free

spin

View down the c axis complex

of

Li...Li

= 324.5,

permission

the

of

value.12891

the unit

phthalocyanine Li...N

from J.

cell

of

radical:

the

lithium

Dimensions

= 194.2pm (reproduced

Chem. Sot..

by

Chem. Commun.,

(1986)962).

1.4.9.6

Solution

The nature

of

Chemistry the species

present

derivatives

has been probed

a number of

investigators.t239,290-2941

n.m.r.

spectroscopic

selection

of

toluene,

Reed,

amido-

using

in solutions high

and cryoscopic and imido-lithium

Snaith

field

of

n.m.r.

From the studies

lithium

of

derivatives

et a112391 have concluded

techniques results

of

by -‘Li

a representative in benzene that

and

more diverse

92 behaviour Thus

is

while

some

association and

often

observed

of

the

states

dimeric others

[(“Bu)C,H,NLi.(py)zl), also

involving

[f”Bu),C=NLi.hmpal, (dimeric rearranging

to have

and

monodiamine

by

and

consistent

identical

with

and

coordination

form

intramolecular

both

been

in

obtained

6Li-1H

by

tetramer

unusually between

mixture

short

contact

supported

the

“dimer” that

the

Ph=MeSiLi exchange responsible

Li

for

and

the

pendant the

for

H(C,) Li-H

reveals

of

(141) 7Li

related

in

collapse

n.m.r.

-Li-‘H

HOESY

For

which

the

and

indicate

Li...H of

are

for

the mixed

that

molar

the but

mixtures

(Ph,SiLi, supports

structures ‘Li

1:l

1:l

solvated

distctnce,

study

phenylsilyllithiums

the

a

reveals

observations

be activated.[2921

of

the be

distance

(f40f

2-Methf

in to

should

and

spectra

experiments.

H(C,)

for

signals

by

have

short

These

monomeri,c

completed

C,D,

distances a

shortest

be

13C n.m.r.

and

are

tetrahedral

to

n.m.r.

in thf

between

the about

atoms

and

however,

(141)

Li

groups.

2-D

the

[CloH7Li.enlZ

the

the

trimeric

alkoxy ‘H

from

HfCe).

(en),]

et for

brought

the

MNDO calculations

exhibits

or PhMezSiLi) mechanism

of

also

of

is

the

assumed

reagents,

temperature

two structurally

which

two

CH,Li,

(140)

8-position

A variable of

,

of

is

of

peaks

dimer,

fC,,H,Li

in

I-lithionaphthalene.tmeda.

results

1-lithionaphthalene

former

structure

for

between the

atom

a1[2921

it

data

interactions.

the

some

(<350pm);

of

by

2-position

cross

H(C,)

the

l-lithionaphthalene

et

indicating

and

molar

and

before

3-lithio-1.5dimethoxypentane

assignments

Schleyer

short Li

of

complex

Snaith

n.m.r.

a Li 2 C 2 core;12911 Li

one

Reed, 7Li

rigid

for

the

thf-de

HOESY exhibits

“BuLi

of of

structural “BuLi

whereas

structure

coordination

Complete for

part

and

N’-benzyl-N,N-dimethylethylene

N...Li data

a dimeric

geometry

dimeric

on dissolution

and

a totally

n.m.r.

monomeric

(tetrameric and

donor

‘H

of

that

with

solid

concentration-dependent

a monomer.!2391

inter-molecular

temperature

in

species

from

solutions

their

and

products

tetrameric

intraLow

are

arene

is

and

state.

[PhN(H)Li.hmpal,

loses

concluded

solid

retain

t~C,H~I)zNLi.hmpalz~

trimer

dilithiated

in

latter

a also

the

[(MezN),C=NLil,

[(PhCH2)2NLi13,

and

in

essentially

engage

[(Ph~H=)=NLi.OEt~l~}

al.!2901

than

[Ph(tBulC=NLils,

monomeric

trimeric

[PhzC=NLi.py14.

solution

components

[hexameric

[(PhCH,),C=NLil,,

equilibria

in

a bimolecular

as

being

of

the

two

a

93 The

species.12931 mainly

ionic

Li...Si

involvement 7Li

is

and

‘lB

interaction,

also

provide

although

some

cryscopic

spectroscopic,

indicate

and

data

support

for

a

orbital

indicated.[2931 n.m.r.

measurements lithium

experimental

that

LiBF,.4hmpa

tetrafluoroborate

and

exists

components

in

held

conductometric solution

together

as by

tight

Li...F

interactions.[2941 Evidence as

Na’), lithium

for

as

and

is

treatments

of

association allow

The

for

rate

of

formation

of

compounds

formation

the

of

the

Reaction

-3OkJ.mol-‘,

of

bromotrichlorosilane or

it

by

chemical

shift

was

protonation

PhLi)

of usually

give

cation

treatments

M’A-M-.12951 tetrameric

[MeO(CH,),CH(R)Lil,

its

it

is

enthalpy

-4lkJ.molV’.

2,4,6-tri(t-butyl)-

195K

in

thf

affords

trichloro-

trichlorosilane

characterised Normal

by

rather

which

a Y3i

metallating

substituted

= H,Me; the

analogue the

with

as

of

organolithium

n = 2,

n = 3,

(R

comparison

3-methoxy-

for

detected

30.9ppm.

(A-1

where

of

by

or

of

reactant

triplets

benzene

at

and

= Li’

This

these

unsubstituted

mesityllithium

silyllithium;[2971 obtained

for

ion

type

whereas

is

anionic

conditions

etheration

in

(M’

solutions

quantitative

accuracy

the

4 and

4:[2961

phenyllithium

*BuLi,

of

determined

to an

total

of

[CH,(CH,),CH(R)Lil

difference

of

dmf

reported.12951

under

intramolecular

been

[MeO(CH,),CH(R)Lil

been

reaction

For

n = 2,3)

tetramer

has

M-A-M’ in

significance

important. the

of

triplets pairs

(RX)

organolithium

enthalpies

ion ion

electrophile

enthalpies

have

of and

particular

the

is

ions

aryloxides

of

a neutral

must

presence

free

sodium

observation

with

the

well

agents than

is

n.m.r. (“BuLi,

deprotonated

products.12971 Lithiation using

of

“BuLi

x = 2, were

y =

the

yields 1.2:

aminosilanes

Me,_,Si(NH(“Bu)I,

(lCxC4)

Me,_,Si(NH(“Bu)),(NLi(“Bu))*_~ x = 3,

characterised

by

y = i.r.

1-3; and

x = 4, ‘H and

(x y =

7Li

l-4);[2981 n.m.r.

=

1, the

y = 0; products

spectroscopic

techniques. The the

addition

of

relatively

slow

dilithioalkenes;[2991 (238K;

2h)

to

give

lithium (293K; cyclic

to

acyclic

48h)

alkynes

formation

alkynes

cis-dilithiocycloalkenes.

react

in

of

ether

results

insoluble

trans-

much more

rapidly

in

94 1.4.10

Sodium

Only

eight

discussed

Derivatives

papers[265,300-3061

after

earlier

in

report

the

consideration

the

review;

results

exception,[3061

of

sulphonate

of

et

the

carboxylate

al.

have

hemi-

seven

The

oxygens

irregular

the

the

each

monodentate

anions and

Na(21...0

two

a

lower

and

that

the

Na’

molecular

(and

but

six

coordinated

(Na...O

(Na...O

= 241.lpml contains

similar,

provided

by

an

Na

four

Na(21...0

(Na(ll...O

= in

two

structurally

oxygens

by

=

anions

(Na...O

structures

dodecyl

is

= 237.1-247.1;

in

(in

methods,

for

sodium

monodentate

molecules

= 236.5,242.3pml

salts

suggest

anions

molecule

(Na(ll...O water

the

n.m.r.

hemihydrate[3001 bidentate

by

bile

affinity

monohydratet3011

coordinated

to

using

of

independent,

is

CaZ’l

crystal

two

water

In the

glycocholate.

the

two

The

crystallographically

246.0pm)

in by

geometry.

atoms:

bearing

Na atom

and

(and

be

one13061

of

constants

has

255.8/294.3pml,

227.8,242.0pml

Na’

to

covered

bar

analyses.

mono-hydratesI

provided

231.51305.4;

xrd

remain

topics

investigation

taurocholatel

described

and

specialised

dissociation

taurocholate

the

sulphate.

an of

and

derived

bearing

than

Coiro

of

binding

chemistry

a11[265,300-3051

crystal

results

the

the

reported;

Caz+l

single

sodium

the

these,

glycocholate

particular,

of

of

of the

thermodynamics

are

on

= 233.9-

= 237.2,249.9;

a distorted

octahedral

arrange-

ment. Croth

has

propenal two

reported

the

sesquihydrate.[3021

Again

crystallographically

atoms

; they

spheres

are

by

Na(21..

(Na(ll...O

in

atom

the

two

approximately

oxygens

coordination

unit

structurally

separate and

polyhedra

in

the

sodium

N-chloro-4-methylbenzenesulphonamide

trihydratei3041

In the

227.3-244.0pml a water latter

and

molecule salt,

octahedrally

the

Na atom one

(Na...O

former is

salt,

surrounded

nitrogen

by

an

oxygen

salts

of

and differ

[CH,.CO.NSO,.C,H,NH,I_Na+,by

(Na...N

= 229.6pml

ICl.NSO,.C,H,CH,l-Na’.[3041 coordinated

=

molecules

= 240.1-248.4pml.

monohydrateI3031

considerably.

(Na(ll...O

water

N-(4-aminobenzenesulphonyllacetamide

H,0,[3031

Na

coordination

anions four

contains similar,

octahedral

from

Na(21...0

3-hydroxy-2-

asymmetric

but

.O = 245.8.247.5pml

= 238.8-239.5; Na

of

independent,

located

generated

242.4,248.1;

The

123K structure

in

three

oxygen8

= 261.3pml a 5-fold the (Na...O

(Na...O from

array. Na atom

anions In

is

= 236.5pml

= and

the

roughly and

a

95 chlorine water

.Cl

(Na.. molecules

Two

= 315.3pm) (Na...O

structure

of

the

hydroxyl

independent

disodium

in

a distorted of

a

hydroxyl

and

four

oxygen

four

is

ligated

of

atom: two

of

instead oxygens

oxygens (Na..

of

As

the

seven

water

does

in

sugar

a

single

the

= 233.0-247.6pm). a CH,Cl,

oxidation

solution

of

not

In

in

the

encapsulate a

the

tetrahedral

= 230.2pm)

and

the

Na

fashion

.O = 217.7,223.7pml

(Na..

(Na...O

were

these

et

studies these

in

and

butanol

by

by the

molecules

is

current

the

and by

suggest

like

“BuK

tmeda; Low

for

rubidium of

by

of

the

the

data

various

significance. by

metal-metal

t-amylate. of

this total

majority

covered

solid

reagent.

that,

a

none vast

and

potassium

addition

to

search;

adequately interest

prepared

metallation

thf

pertinent

literature

Clearly,

“BuLi

Derivatives

papers

potassium,[307-3131

have

hexane

effective in

of

Caesium few

the

elements

a113071

between

solubilised an

during for

topics

Schleyer

and very

caesium.[3141

for

exchange

found

abstracted

for

reported

reviews,

were

specialised

It the

can

temperature

“BuNa.

“BuK

thioamides

has

be

resultant

is

solution n.m.r.

monomeric

under

conditions.[3071

Complexation n.m.r. (-1

the

coordinated

with by

sugar

of

surrounded

Rubidium

earlier

one

or

is

the

by

(E).[265]

tripodand

in

two

(Na...O

crystals

tripodand

latter

the

Potassium, for

subsection

is

the

the of

four

.O = 229.3pml.[2651

1.4.11

and

(1421,

is

NaBPh,

[(Ph,P(0)CH,CH21,NNa.H,0.BuOHI‘BPh~~ structure

by

= 235.3-264.8pml

pyramid

prepared

gave

by

Nat21

molecules

solution

H,O,,

occur

(Na...O

tetragonal

previously

with

and

D-fructose-6-phosphate

molecules

water

a butanol

N(CH,CH,P(OlPh,),,

N(CH,CH,PPh,l,

anions

Na atoms

arrangement,

distorted

and

of

of Nat11

water

octahedral

somewhat

Treatment of

salt

Whereas

oxygens

neighbouring

= 235.4-248.7pml.

crystallographically

heptahydrate.[3051

form

from

K’

by

n-acyl

techniques.13081 results

Z,Z-form

Low

of

in

followed

temperature

with

potassium

bond

cleavage

Addition

by

(<195Kl

of

of

rearrangement

KSCN to the

complexation reaction

of of

or

potassium

naphthalenide

formation

of

and

studied

solutions

E.Z-n-acyl the

(145)

and

(-1

been

in

thf

(1491

of

(1431

thioamide

cation 13091

using

and

(scheme

to 91.

(146)[3101

results respectively.

in

P-P

96

Scheme 9: (143) R = Me; (144) R = Et In the case of (147)[3101 under analogous conditions the P-N bond fractures to give (150). (*Bu)-P -

At higher temperatures (>195K) (148)

("Bu)-P -

P-(tBu)

\/

\/ B I N('Pr)=

P-(+Bu)

7

/\

Me

$Pr

(147)

(146)

1

-P-("Bu)

\/

=-2K'

("BukP-

1

-P-(*Bu)

\/ C

B

/\ Me

N('Prjz (148)

Me (149)

(tBu)-P-

P-(*Bu)

\/

C

Me

(145)

('Bu)-P-

(*Bu)-P -

1

NH(%Pr)

\/ P ('Bu)

-K'

=-2K'

97 interconverts

into

the

asymmetric

BHN(1Pr),]-K’.[309]

whereas

phosphides

KHP(*Bul

and

29BK.13101

All

n.m.r.

compound

(149)

[*BuP--P(“Bu)-

decomposes

KP(tBul(‘Prl:[3101

reagents

and

into

the

(150)

products

were

is

mono-

stable

to

characterised

by

SIP

spectroscopy.

The (1511

synthesis has

example

been

of

reported

and by

metal

structure

depicted

12.

by

analysed

or

characterisation Jutzi,

alkali

treatment

potassium

Figure

structural

a base-free

crystallised Prepared

and

Pohl

metal

using

of

single

in

12.

Figure

crystal

in

xrd

is

the

to

be

It

molecular

from

Angew.

with

comprises

structure

a

of

it

Int.

has

the

“supersandwich

potassium

(reproduced Chem.,

first

methods.

toluene,[311]

trimethylsilylcyclopentadienide permission

it

trimethylsilylcyclopentadiene hydride

and

al;13111

[(Me,Si)C,H,K]

cyclopentadienide

potassium

Crystal

et

of

Ed.

by

Engl..

26(198715831.

complex”

which

(on

sides)

both

is

made

V-&H5

up

of

rings.

a

repeating The

sequence

average

K...C

of

K atoms

contact

and (K...C

98 = 298.8-307.9: between weak

the

K atom

K-(nZ-CsHs)

strands

(K..

ally

ring

centre

n-systems

The K atoms

of

potassium crystal

a distance

An additional between

results found

in for

an electrostatic

the

to

-278pm. occurs

it

distances

and

in

corresponds

relationship

interatomic indicating

large,

anionic

and

bonding

.C = 366.6,367.8pml;

The

shape.

= 300.1-307.4pml

K’...C

neighbouring

their

(1511

zig-zag are

interaction

exception-

between

cations.[3111 structures

4-amino-1-napthalenesulphonic

acid

of

the

(1521[3121

potassium and

of

dihydro-4,4-dimethoxy-5,7-dinitrobenzofurazan-3-oxide (l/l)

adduct

(153)[3131

crystallographically of

(152)[3121

anions

surrounded

The two

K atoms

by seven

.O = 274.7-285.6:

in each

oxygens

K(Z)...0

asymmetric

from

four

unit

separate

= 275.6-290.0pm)

l-

NH,

of

methanol

7-coordinate.

independent are

(K(l)..

are

salts

1,4-

in

l-

NO,

K’

K+.CH,OH

0,N

(153) pentagonal located three

bipyramidal in a cage

anions

molecules In the

of

(K..

(K..

the

structure

cage

formed

the

bromine

Cs atoms

by two

320.7pml

as

bromines

(Cs..

.Br

caesium

which

other

in

(153113131

are

provided

two

by solvent

six

the

neighbours is

oxygens

= 365.lpml.

are

on the

centres. it

has

with

six six

somewhat

.O = 324.4pml

and

the

trigonal

enclosed (Cs...O more

distorted

by a puckered

two

asymmetric of

is

oxygens its

contains

per

3 axes

Cs(ll

completing

surrounded (Cs..

which units

in a =

remote 12-fold

hexagonal two

bromines

is by

tris(N-bromosuccinimide)-

formula

atoms

= 394.6pml

Cs(21 of

at

complexes:

nearest

coordination. .Br

of

independent

central

with

(Cs..

the

of

Cs[Br(CO.CH&H,.CO.N.Br),1[3141

cell

bipyramid

five

.O = 274.4-285.1pm)

crystallographically unit,

The K atom

oxygens,

.O = 271.9.275.9pm).

crystal

bromatetl-1,

arrangements. seven

99

REFERENCES

10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26

P.Hubberstey, Coord. Chem. Rev., 85(1988)1. S.B.Dawes, D.L.Ward, R.H.Huang and J.L.Dye, J. Am. Chem. sot., 108(198613534. S.B.Dawes, A.S.Ellaboudy and J.L.Dye, J. Am. Chem. Sot., 109(198713508. R.N.Edmonds. D.M.Holton and P.P.Edwards, J. Chem. Sot., Dalton Trans., (19861323. A.S.Ellaboudy, D.M.Holton, R.N.Edmonds and P.P.Edwards, J. Chem. Sot., Chem. Commun., (198611444. T.Saji, K.Aoki, K.Suga, M.Fujihiva and S.Aoyagui, Bull. Chem. Sot. Japan, 59(198612623. K.Aika, T.Moriyama, N.Takasaki and E.Iwamatsu, J. Chem. Sot., Chem. Commun., (198611210. J.Nunan. K.Klier, C-W.Young, P.B.Himelfarb and R.C.Herman, J. Chem. Sot., Chem. Commun., (19861193. I.L.C.Freriks, P.C. de Jong-Versloot, A.C.T.C. Kortboek and J.P.van den Berg, J. Chem. Sot., Chem. Commun.. (19861253. R.Tabeta, M.Aida and H.Saito, Bull Chem. Sot. Japan, 59(198611957. I.R.Beattie and K.R.Millington, J. Chem. Sot., Dalton Trans., (1987I1521. S.Suzer and L. Andrews, J. Am. Chem. Sot., 109(19871300. O.Ayed. A.Loutellier, L.Manceron and J.P.Perchard, J. Am. Chem. Sot., 108(1986)8138. L.Bencivenni, L.D'Alessio, F.Ramondo and M.Pelino, Inorg. Chim. Acta. 121(1986)161. L.Bencivenni, F.Ramondo, R.Teghil and M.Pelino, Inorg. Chim. Acta, 121(1986)207. B.Silvi, O.Ayed and W.B.Person, J. Am. Chem. Sot., 108(198618148. M.E.Bedrina, D.N.Glebovskii and V.M.Tret'yak, Russ. J. Inorg. Chem., 31(1986)465. A.Banerjee, A.Quigley, R.F.Frey, D.Johnson and J.Simons, J. Am. Chem. Sot., 109(198711038. P. von R. Schleyer and T.Clark, J. Chem. Sot., Chem. Commun.. (198611371. A.S.Zyubin. A.A.Corbik and O.P.Charkin, Russ. J. Inorg. Chem., 31f19861621. R.S.Tsekhanskii. V.C.Skvortsov, A.K.Molodkin and L.I.Vinogradov, Russ. J. Inorg. Chem., 31(19861903. P. von R. Schleyer, E.Kaufmann, A.J.Kos, T.Clark and J.A.Pople, Angew. Chem., Int. Ed. Engl., 25(19861169. A.Rajca, A.Streitwieser and L.M.Tolbert, J. Am. Chem. sot.. 109(1987)1790. W.R.Winchester, W.Bauer and P. von R. Schleyer, J. Chem. Sot., Chem. Commun., (19871177. T.Clark, J. Chem. Sot., Chem. Commun., (198611774. J.Kaneti. P. von R. Schleyer, T.Clark, A.J.Kos, C.W.Spitznegel, J.C.Andrahe and J.B.Moffat, J. Am. Chem. Sot.. 108(198611481.

100

27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54

E.Kaufmann, P. von R. Schleyer, S.Cronert, A.Streitwieser and M.Halpern. J. Am. Chem. Sot., 109(198712553. D.A.Bors and A.Streitwieser, J. Am. Chem. Sot., 108fl98611397. S.M.Bachrach and A.Streitwieser, J. Am. Chem. Sot., 108(198613946. M.L.McKee, J. Am. Chem. Sot., 109(1987)559. A.Maercker,T.Craule and W.Demuth, Angew. Chem., Int. Ed. Engl., 26(198731032. Y.Apeioig, T.Clark, A.J.Kos, E.D.Jemmis and P. von R. Schleyer, Israel J. Chem., 20(1980143. H.C. von Schnering, M.Schwartx and R.Nesper, Angew. Chem., Int. Ed. Engl., 25(1986)566. C.Kliche, M. Schwarz and H.G. von Schnering, Angew. Chem., Int. Ed. Engf., 26(19871349. J.Evers, G.Oehlinger, G.Sextl and H.-O.Becker, Angew. Chem., Int. Ed. Engl., 26(1987176. P.Bottcher and R.Kelier. Z. Anorg. Allg. Chem., 542(19861144. R.J.Batchelor. T.Birchall and R.C.Burns, Inorg. Chem., 25(198612009. P.A.A.Klusener, L.Brandsma, H.D.Verkruijsse. P. von R. Schleyer, T.Friedl and R-Pi, Angew. Chem., Int.'Ed. Engl., 25(19861465. M.Kilner and G.Parkin, J. Organomet. Chem., 302(1986)181. M.Baudler, Angew. Chem.. Int. Ed. Engl., 26(1987)419. M.Baudler, D.Duster and D.Ouxounis, Z. Anorg. Allg. Chem., 544(1987187. M.Baudier, D.Duster and J.Germeshausen, Z. Anorg. Allg. Chem.. 534fl986119. M.Baudler and D.Duster, Z. Naturforsch., Teil B, 42(19871335. M.Baudlar and D.Duster. Z. Naturforsch., Teil B, 42(19871330. V.Manriquex, W.Honle and H.G. von Schnering, Z. Anorg. Allg. Chem., 539(1986)95. H.Sabrowsky, A.Thimm, P.Vogt and B.Harbrecht, Z. Anorg. Allg. Chem., 546(1987)169. J.Y.Andersson and M.Azoulay, J. Chem. Sot., Dalton Trans., (19861469. H.Kisch, A.Fernandex and R.Millini, Chem. Ber., 119(198613473. R.Steudel, G.Holdt and R.Nagorka, Z. Naturforsch., Teil B, 41(198611519. W.Schnick and M.Jansen, 2. Anorg. Allg. Chem.. 532(1986137. S.V.Chixhevskii and Yu.Ya.Kharitonov, Russ. J. Inorg. Chem.. 31~198611111. A.C.Belch, M.Berkowitz and J.A.McCammon, J. Am. Chem. sot., 108(198611755. O.A.Karim and J.A.McCammon, J. Am. Chem. Sot., 108f198611762. P.Coralski and M.Chabanel, Inorg. Chem., 26(198712169.

101

55 56 57 58 59 60 61 62 63 64 65 66 67 68 69

70 71 72 73 74 75 76 77 78 79

80 81 82 83

R.R.Rhinebarger. J.W.Rovang and A.I.Popov, Inorg. Chem., 25(198614430. W.Weppner, W.Welzel, R.Kniep and A.Rabenau, Angew. Chem., Int. Ed. Engl., 25(1986)1087. Acta I.R.Hill, D.E.Irish. N.J.Taylor and C.E.Toogood, Crystallogr., C42(1986)404. K.-F.Tebbe and U.Georgy, Acta Crystallogr.. C42(1986)1675. B.Harbrecht and H.Jacobs. 2. Anorg. Allg. Chem., 546(1987)48. H.Jacobs, B.Mach, A.-D.Lutz and J.Henning, Z. Anorg. Allg. Chem., 544(1987128. H.Jacobs, B.Mach, B.Harbrecht, H.-D.Lutz and J.Henning, 2. Anorg. Allg. Chem., 544(1987)55. J.Emsley and D.A.Johnson, Polyhedron, 5(1986)1109. D.Mootz and D.Boenigk, J. Am. Chem. Sot., 108(1986)6634. H.-O.Cullmann and H.-U.Schuster, 2. Anorg. Allg. Chem., 537(198617. I.Grund, G.Zwiener and H.-U.Schuster, 2. Anorg. Allg. Chem., 535(1986)7. W.Bronger. P.Muller, R.Hoppner and H.-U.Schuster, 2. Anorg. Allg. Chem., 539(19861175. W.Weise and H.-U.Schuster, Z. Anorg. Allg. Chem., 535(19861143. H.G. von Schnering, J.Wolf. D.Weber, R.Ramirez and T.Meyer, Angew. Chem., Int. Ed. Engl., 25(19861353. E.Seipp and R.Hoppe, 2. Anorg. Allg. Chem., 538(1986)123. R.Baier and R.Hoppe. Z. Anorg. Allg. Chem., 546(1987)122. E.Seipp and R.Hoppe. Z. Naturforsch., Teil B, 41(198611513. P.Kroeschell and R.Hoppe. 2. Anorg. Allg. Chem., 537f19861106. R.Wolf and R.Hoppe, 2. Anorg. Allg. Chem., 539(19861127. G.Wagner and R.Hoppe, Z. Anorg. Allg. Chem., 537(1986)115. P.Kroeschell, R.Wolf and R.Hoppe, Z. Anorg. Allg. Chem., 536f1986181. R.Hoppe and W.Scheld, Z. Anorg. Allg. Chem., 546(19871137. G.Wagner and R.Hoppe, Z. Anorg. Allg. Chem., 549(1987126. R.Hoppe, P.Kroeschell and R.Wolf, Z. Anorg. Allg. Chem., 537(1986)97. E.Seipp and R.Hoppe, Z. Anorg. Allg. Chem., 549(1987)119. R.Luge and R.Hoppe, Z. Anorg. Allg. Chem., 534(1986161. K.Hobbie and R.Hoppe, Z. Anorg. Allg. Chem., 535(1986120. R.Wolf and R.Hoppe, Z. Anorg. Allg. Chem., 536(1986177. V.B.Nalbandyan and I.L.Shukaev, Russ. J. Inorg. Chem., 32(1987)453.

102

84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99

100 101 102 103 104 105 106 107 108 109

J.Vins, M.Urbanova, J.Subrt, V.Zapletal, A.A.Zakharov and I.S.Shaplygin, Coll. Czech. Chem. Commun., 51(1986)809. I.'S.Shaplygin, M.I.Gadzhiev and V.B.Lazarev, Russ. J. Inorg. Chem., 32(19871418. I.S.Shaplygin and M.I.Cadzhiev, Russ. J. Inorg. Chem., 32f19871454. V.L.Volkov and A.A.Ivakin, Russ. J. Inorg. Chem., 31(1986)254. A.A.Vashman, I.S.Pronin, L.V.Colubeva, N.V.Porotnikov and K.I.Petrov, Russ. J. Inorg. Chem., 32(19871796. N.V.Porotnikov, V.V.Ganin, N.M.Gerardi, L.V.Colubeva and K.I.Petrov, Russ. J. Inorg. Chem., 32(19871764. G.Dittrich and R.Hoppe. 2. Anorg. Allg. Chem.. 371(19691306. K.O.Klepp and W.Bronger, Z. Anorg. Allg. Chem., 532(1986)23. K.O.Klepp, Z. Naturforsch., Teil B. 42(1987)130. C.Meyer and T.Schleid, Inorg. Chem., 26(1987)217. V.V.Krylov, A.L.Chistov, E.M.Shulenina and N.N.Stepareva, Russ. J. Inorg. Cheat.. 31(198611564. O.G.Cromov. L.A.Kameskaya and V.T.Kalinnikov, Russ. J. Inorg. Chem., 32(19871137. M.Feist, D.Hass and V.Briehn. Z. Anorg. Allg. Chem., 542(19861223. V.V.Safonov and V.A.Mireev, Russ. J. Inorg. Chem., 31(1986)1714. A.K.Molodkin, A.M.Karagodina, S.B.Nechitailov. A.G. Dudareva and A.G.Krokhina, Russ. J. Inorg. Chem., 31(19861449. A.K.Molodkin. A.M.Karagodina, A.G.Dudareva, S.B. Nechitailov and A.I.Ezhov, Russ. J. Inorg. Chem., 31(198611373. A.K.Molodkin. A.M.Karagodina, A.G.Dudareva, S.B. Nechitailov and A.I.Ezhov, Russ. J. Inorg. Chem., 32(19871772. A.K.Molodkin and A.G.Dudareva, Russ. J. Inorg. Chem., 31(198611603. Z.B.Mukhametshina, V.V.Parakhin, V.P.Seleznev and A.M.Chekmarev, Russ. J. Inorg. Chem., 31(1986)1262. G.Friedrich, H.Fink and H.J.Seifert. Z. Anorg. Allg. 548(19871141. Chem., K.-H.Wandner and R.Hoppe, Z. Anorg. Allg. Chem.. 549(198717. J.C.Dewan. A.J.Edwards and J.J.Guy, J. Chem. Sot., Dalton Trans., (198612623. D.Kissel and R.Hoppe, Z. Naturforsch.. Teil B, 42(1987)135. K.-H.Wandner and R.Hoppe, Z. Anorg. Allg. Chem., 546(19871113. D.Kissel and R.Hoppe, Z. Anorg. Allg. Chem., 540/541(19861135. W.Massa, Acta Crystaflogr., C42119861644.

103

110 111 112 113 114 115 116 117 118 119 120 121 122 123 124 125 126 127 128 129 130 131 132 133 134 135 136 137

H.P.Beck and W.Milius, 2. Anorg. Allg. Chem., 539(1986)7. B.Leuenberger, B.Briat, J.C.Canit, A.Furrer. P.Fischer and H.U.Cudel, Inorg. Chem., 25(198612930. W.Preetz and H.J.Steinebach, 2. Naturforsch., Teil B, 41(19861260. P.W.Smith and R.Stranger, Aust. J. Chem., 39(1986)1269. H.Nakayama, N.Nakamura and H.Chihara. Bull. Chem. Sot. Japan, 60(1987)99. C.Reber and H.U.Cudel, Inorg. Chem., 25I198611196. E.Herdtweck, W.Massa and D.Babel, 2. Anorg. Allg. Chem. 539(1986187. C.Meyer, S.-J.Hwu and J.D.Corbett, 2. Anorg. Allg. Chem., 535(19861208. D.Kissel and R.Hoppe, 2. Anorg. Allg. Chem., 532I1986117. I.E.Cray, I.C.Madsen, S.E.Butler, P.W.Smith and R.Stranger, Acta Crystallogr., C42(1986)769. P.W.Smith, R.Stranger and I.E.Cray, Inorg. S.E.Butler, Chem., 25(1986)4375. S.T.Bramwell, P.Day. M.T.Hutchings, J.R.C.Thorne and D.Visser. Inorg. Chem., 25(1986)417. M.C.Kanatzides and T.J.Marks, Inorg. Chem., 26(1987178. M.-H.Whangbo and L.F.Schneemeyer, Inorg. Chem., 25(1986)2424. A.J.Schultz, H.Horiuchi and H.B.Krause, Acta Crystallogr., C42I19861641. A.Hussain and L.Kihlborg. Acta Chem Stand., Ser.A, 41(1987)18. E.Cocke, R.Schollhorn, C.Aselmann and W.Mullerwarmuth, Inorg. Chem., 26(198711805. Yu.V.Mironov, P.P.Samoilov. V.E.Fedorov, V.I.Lisoivan and S.A.Cromilov, Russ. J. Inorg. Chem., 32I19871622. C.Meyer, S.-J.Hwu, S.Wijeyesekeva and J.D.Corbett, Inorg. Chem., 25(1986)4811. U.V.Varadaraju, K.A.Thomas, B.Sivasankar and C.V.Subba Rao, J. Chem. Sot., Chem. Commun., (1987)814. K.Kasatani and H.Sato, Chem. Letters, (19861991. R.E.Mulvey. W.Clegg. D.Barr and R.Snaith, Polyhedron, 5(198612109. L.Echeverria, M.Delgrades, V.J.Catto, C.W.Cokel and L.Echegoyen, J. Am. Chem. Sot., 108(198616825. Y.Sakai, M.Shinmura, H.Otsuka and M.Takagi, Bull. Chem. Sot. Japan, 60(1987)545. C.Smith, E.J.O'Reilly and C.H.L.Kennard, Acta Crystallogr.. C42(198611329. C.Smith, E.J.O'Reilly and C.H.L.Kennard, Polyhedron, 6(1987)871. F.Bongardt, F.Vogtle, D.Wegmann, D.Ammann, T.Maruizumi and W.Simon, Helv. Chim. Acta, 70(19871153. E.Metzger, R.Aeschimann, M.Egli, C.Suter, R.Dohner, D.Ammann. M.Dobler and W.Simon. Helv. Chim. Acta. 69(1986)1821.

104

138 139 140 141 142 143 144 145 146 147 148 149 150 151 152 153 154 155 156 157 158 159 160 161 162 163 164 165 166

K.Ueno, K.Hiratani, K.Taguchi, T.Okada and H.Sugihava, J. Chem. Sot., Chem. Commun., (19871949. J.M.Miller, S.J.Brown, R.Theberge and J.H.Clark. J. Chem. Sot., Dalton Trans., (198612525. D.J.Cram, Angew. Chem., Int. Ed. Engl., 25f198611039. A.Rodrigue. J.W.Bovenkamp, B.V.Lacroix, R.A.B.Bannard and G.W.Buchanan. Can. J. Chem., 64(19861808. A.Yu.Tsivadxe, V.A.Trofimov and N.B.Generalova, Russ. J. Inorg. Chem., 31(19861179. A.Yu.Tsivadxe, N.B.Generalova and E.N.Pyatova, Russ. J. Inorg. Chem., 31(198619. R.B.Dyer, R.C.Chirardelli, R.A.Palmer and E.M.Holt, Inorg. Chem., 25(198613184. S,Kamitori, K.Hirotsu and T.Higuchi. J. Am. Chem. Sot., 109(198712409. J.H.Burns and R.M.Kessler, Inorg. Chem. 26f198711370. M.Tahiri, P.Doppelt, J-Fischer and R.Weiss, Inorg. Chim. Acta, 127(1987)Ll. A.Bianchi, J.Ciusti. P.Paoletti and S.Mangani, Inorg. Chim. Acta, 117(19861157. M.B.Gholivand and M.Shamsipur, Inorg. Chim. Acta, 121(1986)53. M.B.Cholivand, S.Kashanian and M.Shamsipur, Polyhedron, 6(19871535. H.D.H.Stover, M.Robillard and C.Detellier, Polyhedron, 6f19871577. G:Rounaghi and A.I.Popov, Polyhedron, 5(1986)3329. G.Rounaghi and A.I.Popov, Inorg. Chim. Acta, 114(1986)145. R.D.Boss and A.I.Popov, Inorg. Chem., 25(198611747. T.M.Fyles, Can. J. Chem., 65(1987)884. B.G.Cox, E.Buncel, H.S.Shin, R.A.B.Bannard and J.G.Purdon, Can. J. Chem., 64(1986)920. Y.Takeda and A.Tanaka. Bull. Chem. Sot. Janan. I, 59(19861733. Yu.G.Mamedova, Z.O.Tuarsheva and A.L.Shabanov, Russ. J. Inorn. Chem.. 31(19861428. M.Sakim, T.Hayashita, T.Yamabe and M.Igawa, Bull. Chem. Sot. Jspan, 601198711289. S.Yoshida and S.Hayano. J. Am. Chem. Sot., 108(198613903. T.Kakutani, Y.Nishiwaki, T.Osakai and M.Senda, Bull. Chem. Sot. Japan, 59(19861781. T.Iwachido, H.Naito, F.Samukawa, K.Ishimaru and K.Toei. Bull. Chem. Sot. Japan, 59(198611475. A.F.Danil de Namor and E.Sigstad, Polyhedron, 5(19861839. J.M.Gold, D.M.Teegarden, K.M.XcGrane, D.J.Luca, P.A.Falcigno, C.C.Chen and T.W.Smith, J. Am. Chem. Sot.. 108(1986)5827. A.S.Khan, W.G.Baldwin and A.Chow, Can. J. Chem., 65(198711103. R.D.Gandour, F.R.Froncxek. V.J.Gatto, C.Minganti, R.A.Schultz, B.D.White, K.A.Arnold. D.Haxxocchi. S.R.Miller and G.W.Gokel, J. Am. Chem. Sot., 108(198614078.

105

167 168 169 170 171 172 173 174 175 176 177 178 179 180 181 182 183 184 185 186 187 188 189 190 191

K.A.Arnold, L.Echegoyen, F.R.Fronczek, R.D.Candour, V.J.Catto, B.D.White and G.W.Gokel, J. Am. Chem. Sot., 109(198713716. H.Delgrado, L.Echegoyen, V.J.Catto, D.A.Gustowski and C.W.Gokel. J. Am. Chem. Sot.. 108(1986)4135. L.Echegoyon, D.A.Custowski, V.J.Gatto and G.W.Cokel, J. Chem. Sot., Chem. Commun., 119861220. C.A.Chang, J.Twu and R.A.Bartsch, Inorg. Chem.. 25(19861396. N.Nakashima, I.Moriguchi, K.Nakano and M.Tagaki, J. Chem. Sot., Chem. Commun.. (1987)617. A.P.de Silva and S.A. de Silva. J. Chem. Sot., Chem. Commun., (198611709. G.Sosnovsky, J.Lukszo, P.L.Gutierrez and K.Scheffler, Z. Naturforsch., Teil B, 42(19873376. P.D.Beer, J. Chem. Sot., Chem. Commun., (198611678. P.D.Beer, C.G.Crane, A.D.Keefe and A.R,Whyman. J. Organomet. Chem.. 314(1986)C9. Y.Yano, M.Kimura, K.Shimaoka and H.Iwasaki, J. Chem. Sot.. Chem. Commun.. (19861160. C.Cuinand, P.Marsau, H.Bouas-Laurent. A.Castellan, J.-P.Deavergne and M.Lamotte, Acta Crystallogr., C43(1987)857. C.B.Knobler, E.F.Maverick, K.N.Trueblood, R.C.Helgeson and D.J.Cram, Acta Crystallogr., C42(19861156. H.Bouas-Laurent, A.Castellan, M.Daney, J.-P.Desvergne, G.Guinand, P.Marsau and M.H.Riffaud. J. Am. Chem. Sot.. 108(1986)315. K.Kobiro, M.Takahashi, S.Takada, K.Kakiuchi, Y.Tobe and Y.Odaira, Chem. Letters, (19861455. P.L.Zanonato, P.Di Bernardo, A.Cassol and G.Tanat, Polyhedron, 6(19871417. R.Hendricks, O.E.Sielcken, W.Drenth and R.J.M.Notte, J. Chem. Sot., Chem. Commun., (1986)1464. N.Kobayashi and Y.Nishiyama, J. Chem. Sot., Chem. Commun., fl986Il462. S.G.Bott, A.W.Coleman and J.L.Atwood, J. Am. Chem. Sot., 108fl98611709. C.Calestani, F.Ugozzoli, A.Arduini. E.Chidini and R.Ungaro, J. Chem. Sot., Chem. Commun., (19871344. W.Pangborn, W.Duax and D.Langs, Acta Crystallogr., C43(1987)890. W.Pangborn, W.Daux and D.Langs, J. Am. Chem. Sot.. 109(1987)2163. N.D.Jones, M,O.Chaney, J.W.Chamberlin, R.L.Hamill and S.Chen, J. Am. Chem. Sot., 95(1973)3399. K.Suzuki, K.Tohda, H.Sasakura, H.Inoue, K.Tatsuta and T.Shirai, J. Chem. Sot., Chem. Commun., (19873932. H.Saito and R.Tabeta. Bull. Chem. Sot. Janan. L , 60(1987161. D.L.Ward, R.R.Rhinebargsr snd A.I.Popov, Inorg. Chem., 25(198612825.

106

192

193 194 195 196 197 198 199

200 201 202 203 204 205 206 207

209

210 211 212 213 214 215 216 217 218 219

A.Abou-Hamdan, A.M.Hounslow, S.F.Lincoln and T.W.Hambley, J. Chem. Sot., Dalton Trans., (19871489. S.F.Lincoln, B.J.Steel, I.M.Brereton and T.N.Spotswood. Polyhedron, 511986)1597. S.F.Lincoln, I.M.Brereton and T.M.Spotswood, J. Am. Chem. sot., 108(1986)8134. S.F.Lincoln, E.Horn, M.R.Snow, T.W.Hambley, I.M.Brereton and T.M.Spotswood, J. Chem. Sot., Dalton Trans., (198611075. C.Belin and H.Mercier, J.Chem. Sot., Chem. Commun., (1987)lQO. P.Bottcher and H.Buchkremer-Hermanns, 2. Naturforsch.. Teil B, 42(1987)272. M.Tahiri, P.Deppelt. J.Fischer and R.Weiss, Inorg. Chim. Acta, 127(1987)Ll. G.Rounaghi and A.I.Popov, polyhedron, 5(1986)1935. H.-J.Buschmann, Inorg. Chim. Acta, lZO(l9861125. T.C.W.Mak, W.-H.Yip. C.H.L.Kennard, G.Smith and E.J.O'Reilly, Inorg. Chim. Acta, lll(19861L23. I.Fonseca, S.Martinez-Carrera and S.Carcia-Blenco, Acta Crystallogr., C42(198611123. A.J.A.R.Blankensteyn and J.Kroon, Acta,Crystallogr.. C42(19861291. T.Lis, Acta Crystallogr., C43(1987)16. S.Jaulmes, P.Laruelle and E.Fabregue, Acta Crystallogr., C43(1987)238. D.R.Amstrong. A.J.Banister, W.Clegg and W.R.Gill, J. Chem. Sot., Chem. Commun., (1986)1672. B.Fusser and R.Mattes. 2. Anorg. Allg. Chem., 547(1987)158. U.Nikloweit and R.Mattes, 2. Anorg. Allg. Chem., 532(1986)145. K.V.Titova and I.P.Celyuk, Russ. J. Inorg. Chem.. 32(1987)160. W.Eul and G.Gattow, Z. Anorg. Allg. Chem., 535(19861148. W.Eul and G.Gattow, Z. Anorg. Allg. Chem., 535(1986)159. W.Eul, G.Kiel and G.Gattow, Z. Anorg. Allg. Chem., 535(1986)167. W.Eul and G.Gattow, Z. Anorg. Allg. Chem., 538(1986)151. M.M.Olmstead. P.P.Power and G.Sigel, Inorg. Chem., 25(1986)1027. P.Leoni, E.Grilli. M.Pasquali and M.Tomassini, J. Chem. sot., Dalton Trans., (1986)1041. H.Schumann, W.Genthe, E.Hahn, J.Pickhardt, H.Schwarz and K.Eckart, J. Organomet. Chem., 306(1986)215. R-Goddard, C.Kruger, K.R.Porschke and G.Wilke, J. Organomet. Chem., 308(1986185. J.L.Atwood. S.G.Bott. P.B.Hitchcock. C.Eaborn. R.S.Shariffudin, J.D.Smith and A.C.Sullivan, J, Chem. sot.. Dalton Trans., (19871747. D.J.Brauer, H.Burger and C.R.Liewald, J. Organomet. Chem., 307(19861177.

107

220 221 222 223

224 225 226 227 228 229 230 231 232 233 234 235 236 237 238

239

240 241

242 243

K.Jones, W.Russeler, K.Angermund and C.Kruger, Angew. Chem., Int. Ed. Engl., 25(19861927. Ft.J.Bianchini, U.Ceiser. H.Place, S.Kaizaki. Y.Morita and J.I.Legg, Inorg. Chem.. 25(1986)2129. C.Hasselkus, S.Hietkamp and O.Stelzer, 2. Anorg. Allg. Chem., 534(1986)50. M.Motevalli and C.Wilkinson, A.R.Barron, M.B.Hursthouse, J. Chem. Sot., Chem. Commun., (1986181; J.A.Bandy, A.Berry, M.L.H.Creen and K.Prout, J. Chem. Sot., Chem. Commun.. (1985)1462. M.Motevalli and M.B.Hursthouse, A.R.Barron, C.Wilkinson, J.Chem. Sot., Dalton Trans., (1987)837. S.-C.Shyu, M.Calligaris, C.Nardin and A.Wojcicki, J. Am. Chem. Sot., 109(1987)3617. H.Schumann. E.Palamidis, C.Schmid and R.Boese, Angew. Chem.. Int. Ed. Engl., 25(19861718. and C.Cuastini, F.Arena, C.Floriani. A.Chiesi-Villa J. Chem. Sot., Chem. Commun., (198611369. and S.Ciurli, E.M.Meyer, C.Floriani, A.Chiesi-Villa J. Chem. Sot., Chem. Commun., (19871281. C.Cuastini, C.Floriani, A.Chiesi-Villa and S.Ciurli, S.Gambarotta, C.Guastini. Angew. Chem., Int. Ed. Engl., 25(19861553. F.Arena. C.Floriani and P.F.Zanazzi, J. Chem. Sot., Chem. Commun., (19871183. F.Arena, C.Floriani, A.Chiesi-Villa and C.Cuastini, Inorg. Chem.. 25(198614589. F.Corazza, C.Floriani and M.Zehnder, J. Chem. Sot., Chem. Commun., (198611270. W.Klaui, A.Muller, W.Eberspach, R.Boese and I.Coldberg, J. Am. Chem. Sot.. 109f19871164. S.A.Kingsley, A.Streitwieser and A.Zalkin, Acta Crystallogr.. C42(198611092. J.A.Bandy, A.Berry, M.L.H.Creen and K.Prout, J. Chem. Sot., Chem. Commun., (1985)1462. T.Mashiko, C.A.Reed. K.J.Haller and W.R.Scheidt, Inorg. Chem., 23(1984)3192. W.Clegg, R.E.Mulvey, R.Snaith. C.E.Toogood and K.Wade, J. Chem. Sot.. Chem. Commun., (198611740. M.Geissler, J.Kopf. B.Schubert, E.Weiss, W.Neugebauer and P. von R.Schleyer, Angew. Chem., Int. Ed. Engl., 26(19871587. D.Reed, D.Barr, R.E.Mulvey and R.Snaith, J. Chem. Sot., Dalton Trans., (19861557. D.Barr, W.Clegg, R.E.Mulvey, R.Snaith and K.Wade, J. Chem. Sot.. Chem. Commun., (19861295. D.R.Armstrong, D.Barr, R.Snaith, W.Clegg, R.E.Mulvey, K.Wade and D.Reed, J. Chem. Sot., Dalton Trans., (198711071. B.Tecle, A.F.M.H.Rohman and J.P.Oliver, J. Organomet. Chem., 317(1986)267. P.C.Willard and C.B.Carpenter, J. Am. Chem. Sot., 108(19861462.

108

244 245

246 247 248 249 250 251 252 253

254 255 256 257 258 259 260 261

262 263

264 265 266 267

H.Burger and C.R.Liewald, J. Organomet. Chem., D.J.Brauer, 308(19861119. D.R.Armstrong, D.Barr, W.Clegg, R.E.Mulvey, D.Reed, R.Snaith and K.Wade. J. Chem. Sot., Chem. Commun.. (19861869. C.Fritz and W.Holerich, Z. Anorg. Allg. Chem., 422(1976)104;417(1975)241. M.F.Lappert and A.K.Rai, E.Hey, P.B.Hitchcock. J. Organomet. Chem., 325(1987)1. K.S.Lee, P.C.Williard and J.W.Suggs, J. Organomet. Chem., 299(19861311. C.Kruger and K.Angermund, H.-J.Cais, U.Dingerdissen, J. Am. Chem. Sot., 109(198713775. C.Schmidt, C.Baum, W.Massa and A.Berndt, Angew. Chem., Int. Ed. Engl., 25(1986)111. P.B.Hitchcock, M.F.Lappert and S.J.Smith, J. Organomet. Chem., 320(19871C27. W.Bauer, C.Muller. R.Pi and P. von R.Schleyer, Angew. Chem., Int. Ed. Engl., 25(198611103: L.M.Ennelhardt. B.S.Jollv, P.C.Junk. C.L.Raston. B.W.Skklton and A.H.Whitk. Aust. J. Chem., 39(1986)1337. M.Haase and C.M.Sheldrick. Acta Crystallogr., C42(198611009. IJ.Klingebiel and D.Schmidt, E.Egert. U.Kliebisch. Z. Anorg. Ally. Chem., 548(1987189. R.A.Wanat. D.B.Collum, C. van Dyne, J.Clardy and R.T.DePue. J. Am. Chem. Sot.. 108(198613415. D.Barr, W.Clegg. R.E.Mulvey, R.Snaith and D.S.Wright, J. Chem. Sot., Chem. Commun.. (19871716. C.Boche, M.Marsch and K.Harms, Angew. Chem., Int. Ed. Engl., 25(19861373. R.A.Bartlett. M.M.Olmstead, P.P.Power and C.A.Sigel, Inorg. Chem.. 26(198711941. A.M.Arif, R.A.Jones and K.B.Kidd, J. Chem. Sot., Chem. Commun., (198611440. 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. P.B.Hitchcock, N.H.Buttrus and A.C.Sullivan, J. Organomet. Chem.. 303(19861321. L.M.Engelhardt. J.MacB.Harrowfield. M.F.Lappert, I.A.MacKinnon. B.H.Newton, C.L.Raston, B.W.Skelton and A.H.White, J. Chem. Sot., Chem. Commun., (19861846. M.Marsch, W.Massa, K.Harms. C.Baum and C.Boche. Angew. Chem., Int. End. Engl.. 25(198611011. C.A.Chilardi, P.Innocenti, S.Midollini and A.Orlandini, J. Chem. Sot.. Dalton Trans., (198612075. H.Dietrich. W.Mahdi and R.Knorr, J. Am. Chem. Sot., 108(198612462. I.Erdelmeier. H.J.Lindner and J.Vollhardt, H.-J.Cais. Angew. Chem., Int. Ed. Engl., 25(19861938.

109

268

269

270 271 272

273 274 275 276 277 278 279

280 281 282 283 284 285 286 287 288 289 290 291 292

D.R.Armstrong. W.Clegg, H.M.Colquhoun, J.A.Daniels, I.R.Stephenson and K.Wade, J. Chem. Sot., R.E.Mulvey, Chem. Commun., (19871630. C.Klebe. K.H.Bohn, M.Marsch and C.Boche, Angew. Chem., Int. Ed. Engl., 26I1987178. G.M.Sheldrick and D.Stalke, K.Dippel, U.Klingebiel, Chem. Ber.. 120(1987)611. H.-J.Cais, J.Vollhardt and H.J.Lindner, Angew. Chem., Int. Ed. Engl.. 25119861939. N.H.Buttrus, C.Eaborn, S.H.Cupta, P.B.Hitchcock, J.D.Smith and A.C.Sullivan. J. Chem. Sot.. Chem. Commun.. (198611043. P.Brooks. D.C.Craig, M.J.Gallagher. A.D.Roe and A.Sarroff. J. Organomet. Chem.. 323(1987)Cl. R.E.Mulvey. K.Wade. D.Armstrong, C.T.Walker, R.Snaith, W.Clegg and D.Reed, Polyhedron, 6(19871987. R.A.Bartlett, M.M.Olmstead and P.P.Power, Inorg. Chem., 25(198611243. A.J.Banister, W.Clegg and W.R.Cill, J. Chem. Sot., Chem. Commun., (1987)850. S.Hietkamp and O.Stelzer, J. Organomet. Chem., D.J.Brauer, 299(19861137. A.M.Arif, A.H.Cowley, R.A.Jones and J.M.Power, J. Chem. sot., Chem. Commun., (198611446. N.H.Buttrus. C.Eaborn, P.B.Hitchcock. J.D.Smith, J.G.Stamper and A.C.Sullivan, J. Chem. Sot., Chem. Commun., (19861969. R.Boese and U.Klingebiel, J. Organomet. Chem., 315I1986lC17. U.Schumann. E.Weiss, H.Dietrich and W.Mahdi, J. Organomet. Chem.. 322I19871299. C.Boche, H.Etzrodt, M.Marsch. W.Massa, C.Baum, H.Dietrich and W.Mahdi, Angew. Chem.. Int. Ed. Engl., 25(19861104. R.Hacker, P. von R.Schleyer, C.Reber, C.Muller and L.Brandsma, J. Organomet. Chem., 316(1986)C4. C.E.Herberich. B.Hessner and M.Hostalak, Angew. Chem., Int. Ed. Engl., 25(1986)642. N.Hertkorn, F.H.Kohler, C.Muller and C.Reber, Angew. Chem., Int. Ed. Engl.. 25(19861468. D.D.Bray and N.F.Bray, Inorg. Chim. Acta, lll(1986lL39. V.M.Padmanabhan, V.S.Jakkal and N.S.Poonia, Acta C43(1987)1061. Crystallogr., E.C.Constable, L.-Y.Chung, J.Lewis and P.R.Raithby, J. Chem. Sot., Chem. Commun., (198611719. H.Sugimoto, M.Mori, H.Masuda and T.Taga, J. Chem. Sot., Chem. Commun., (19861962. D.Barr, R.Snaith. D.S.Wright, R.E.Mulvey. K.Jeffrey and D.Reed, J. Organomet. Chem., 325(1987lCl. M.Vos, F.J.J. de Kanter, M.Schakel, N.J.R. van Eikema Hommes and C.W.Klumpp, J. Am. Chem. Sot., 109(1987)2187. W.Bauer, T.Clark and P. von R.Schleyer, .I. Am. Chem. Sot., 109(19871970.

110

293 294 295 296 297 298 299

300 301 302 303 304 305 306 307 308 309 310 311 312 313 314

E.Buncel. T.K.Venkatachalam and IJ.Edlund, Can. J. Chem.. 64(198611674. D.Barr, K.B.Hutton, J.H.Morris, R.E.Mulvey, D.Reed and R.Snaith, J. Chem. Sot., Chem. Commun.. (19861127. C.Calli and L.Mandolini, J. Chem. Sot., M.Crescenri, Chem. Commun.. (19861551. P.J.A.Ceurink and G.W.Klumpp, J. Am. Chem. Sot., 108(1986)538. H.Oehme and H.Weiss. J. Organomet. Chem.. 319(1987)C16. B.J.Aylett and C.-F.Liaw, J. Organomet. Chem., 325I1987191. A.Maercker, T.Craule and U.Cirreser. Angew. Chem., Int. Ed. Engl., 25I19861167. V.M.Coiro, F.Mazza and C.Pochetti, Acta Crystallogr., C42(19861991. V.M.Coiro. M.Manigrasso, F.Maxza and C.Pochetti, Acta Crystallogr.. C43(1987)850. P.Groth. Acta Chem. Stand.. Ser. A, 41(19871117. H.C.Patel and T.P.Singh, Acta Crystallogr., C43I19871844. M.M.Olmstead and P.P.Power, Inorg. Chem., 25(198614057. T.Lis, Acta Crystallogr., C42I198611745. E.Mukidjam, S.Barnes and C.A.Elgavish, J. Am. Chem. Sot., 108(1986)7082. R.Pi, W.Bauer, B.Brix, C.Schade and P. von R.Schleyer, J. Organomet. Chem., 306(1986lCl. M.Raban and C.Shmyr, J. Am. Chem. Sot., 108(198612112. M.Baudler and C.Kupprat, 2. Anorg. Allg. Chem., 533(1986)146. M.Baudler and C.Kupprat, 2. Anorg. Allg. Chem.,. 533(19861153. P.Jutzi, W.Leffers. B.Hampel. S.Pohl and W.Saak, Angew. Chem., Int. Ed. Engl., 26(19871583. C.J.Brown and H.R.Yadav, Acta Crystallogr., C43(198711087. C.K.Lowe-Ma, Acta Crystallogr., C42(1986)38. C.Svensson, J.Albertsson and L.Eberson, Acta Crystallogr., C42(198611500.