Heavier alkali metals annual survey covering the year 1975

133

HEAVIER

ALKALI

ANNUAL

SURVEY

METALS COVERING

THE YEAR 1975

EDWIN M. KAISER Department 65201

of

Chemistry,

University

of

Missouri,

Columbia,

Columbia,

Missouri

(USA)

COilTENTS 1.

Physical

2.

Synthetic

Aspects

3.

Reactions

with

4.

References

PHYSICAL

1.

Organic

Chemical

Inorganic

the

of

with

lithium-formaldehyde

of

I [l]-

also

by differences

Kinetic sodium

have

Annual

These

do not

certain

which

results

with

ion-ketyls

bonding

led

Survey

the

authors

coverinq

to

the

not

pair

the

149

where

studies conclude

year

1975

in

of

contrkst

YO SCF

one minimum correto

those

two stablezspecies

explanations

ion-pairs.

by an -ab initio

presence

only

earlier

and solvation,

and conductometric

has been studied

suggest

are

ion

agree

sodium in

ion pair

results

to

scopy

145

Compounds

1

sponding

but

and Organometallic

ORGANIC CHEMICAL ASPECTS

UHF procedure,

exist.

133 113

The sodium-formaldehyde

the

Aspects

of

concerned

The discrepancies

obtained the

ion-pair

with

spectro-

are

reconciled

respectively.

on ethereal that

the

solutions carbanion

see J.Oryanome:al.Chm.,

of is

polystyryl-

a naked

one and

133(1375)1-38-

131

that the cation Na(DME)*+(II)

in dimethoxyethane

(DME) can be described

by the kinetic

entity

; s

[Z]-

II

papers described

Several

phosphino,

acidities

functional

groups

often

a rough guide

give

carbanion

as tentative,

[3]_

at best.”

the gas phase [4]. species

to carbanion derived

and other

earlier

establishment metric

cussed.

pKa values Indicators

measurements

are ascribe-1

delocalized.

Many earlier of certain available

nitriles

of acidities

kinetic

acidi ties

regarding

rela-

must be regarded

in DPlSO

charge

in these

of the above two papers

paper which describes

the

in DMSOusing a spectrophoto-

pKa’s have now been changed and

compounds as a function to cover

same

and ketones

to the negative

The results

assigned

and compared

those of the same compounds in

ones are summarized in a full

method [5].

different

and even approach

scale

conclusions

of several

thio,

by these

‘*_ _ .at though

stabilities,

The acidities

of an absolute

activated

that

from kinetic

Such results

being extensively

have been determined

conclude

of car-

sulfonyl-contafning

carbon-acids

The authors

have been found to parallel

of certain

molecules

of several

stabilities

work in the area of acidities

acidities

and phenyl-substituted

with the kinetic

tive

additional

Thus, equilibrium

bon acids.

of solvent

the pK range of 8.3

are dis-

to 30.6

in DMSOare

listed. Another group of workers has presented

experimental

of a large

number of anions

derived

from carbon,

DMSO[6]-

Both charge delocalization

and steric

said

to affect

i

the solvation

The trifluoromethylsulfonyl

oxygen,

solvation

enthalpies

and halogen

hindrance

acids

to solvation

in

are

energies. group has been found to lie

between the nitro

135

and benzoyl tion

groups

in its

ihe use of

[7]_

ability

this

and other

and cyclopropyl

isopropyl, an estimate

moieties

to be made of

and thus destabilized.

have also and other

a variety

of substituted

dithianes

unrelated

study,

that of

the kinetic

tritiated

stabilize

and acyclic

conjugative been studied

of

III

indicating

substantially

are strained it

is concluded

with carbanions.

using cesium salts

in cyclohexylamine

acidity

data which allow

systems,

effect

ioniza-

to methyl,

anions

compounds in !lMSO[S],

triphenylmethane

carbanions

quantitative

to which cyclopropyl

a large

of hydrocarbons

groups attached

has provided

Eoth in the cyclic

Equilibrium-acidities

rt-hydrogen atoms towards

functional

the extent

that the S02CF3 group exerts

variety

to activate

and a

and cesium salts

[9]_

Finally,

has been found

in an

to be greater

that alpha-trimethylsilyl

and

than

qroups

[IO]. (=5i)3C3H III

The bridgehead

hydrogen H3, shown in structure

IV, has been found to under-

go exchange

in deuterated

methanol using sodium methoxide

temperature

of 25” [ll].

In contrast,

conditions. authors side

to state

of bridged

enolates

results

ihese

Hl in IV fails

along with those on other

that enolate

stability

chain

low

to exchange under these ring

systems have led the

in such polycyclics

is enhanced at the

boat forms but not at their

in locked

at the remarkably

forms is diminished

bows.

The stability

of similar

considerably.

IV

In

contrast

to

the

corresponding

non-phenylated

systems

V and VI,

the

rl-

c

136 hydrogens of VII and VIII are exchanged with deuterium rate suggesting

that

delocalization The results

the phenyl groups

from C4 to the double are discussed

at virtually

the same

in VII cause the elimination

of charge

bond at C6,7 previously

in relation

to earlier

observed

described

carbonium

in V [12]. ion

chemistry.

The influence

viewed [13]_ tunneling distribution orientation latter

of

ionic

association

Other papers in this

in the elimination

reactions

are noteworthy

reactions

area have addressed

of five

reactions

VIII

in B-elimination

of certain

from E2 reactions of similar

P

VII

VI

V

(j-J’”

a”

0

0

Z-phenylethyl secondary

the question systems

alkyl

in that such eliminations

of hydrogen

[14].

tromides

of Z-butyl-N.N-disulfonimides

hris been re-

the olefin

[15-j, (IX)

afforded

and the [16].

only

The l-

butene.

‘Y RSOR I N\SOZR IX A new type of conversion reactions specifically

1.3-dehydrohalogenation

of species presumably eliminate

like

has been proposed

X to XI effected

proceed

by potassium

via ring-opened

potassium

chloride

intermediates

to afford

to account

r-butoxide

for

[17].

XII which stereo-

trans-products.

the The

__..-_

_r._..

_.

.

..-.

138 In conjugation

100 MHz [243. the authors is

with the NMRspectra

that the proportionality

conclude

of

cation,

phenyl tropyllum

constant

10 ppm/uni t charge

of

open to question. Conformational

mobility

annulene has been studied are interpreted bonds leading

zation

sequence

The cyclodecatrienyl

A full tion

at a higher

and by proton

scopy.

compound undergoes

Such topomeri-

field

abstraction indicates

directly

&positions

rather

than via a Interestingly,

of 5000-G. by reaction

of XX by potassium the presence

electrocyclization

of fenchone

and sodium pyrene

by CIDHP at 60-G [26].

paper appeared which discussed

at the five

toponers.

nine

temperatures

about the neighboring

anion XVIII has been prepared

of the homoenolization

occurs

at various

sodium anthracene,

as evidenced

The NMRspectrum of XVIII at -65” this

between

has been found to occur

such CIDW is not observed

species;

The spectra

chemically.

ttio alcohols

XIX with potassium

of cis,cis,cis,trans-[9]-

of the trans-bond

of sodium naphthalene.

disproportionation

salt

N+iR[25]-

to a dynamic equilibrium

Protonation or

by proton

in terms of rotation

is demonstrated

with water

in the potassium

triene

amide [27].

of a symmetricai

at -41°.

the results

(XXI) [28].

was demonstrated

of

of a detailed That deuterium

examinaexchange

by 13C and ‘H NMRspectro-

_ .

L

139

Other papers describing included

13C NMR of

the following:

LL’9], ‘ii RI!.? of

alky!malonates S-ketoesters

NMRexperiments

hydrocarbon

of

are treated

anion of a nydrocarbon

of

above technique

and the

39 K NMRand a7Rb

species

in the presence

electron

is a %nction

to investigate

to study electron

and its

parent

1361,

of such systems

transfer

exchanges.

peculiarities

transfer

of certain

which

It has

is a function

ihree

The processes

other

oapers

used the

in systems XXII where n = 3 and

between N-n-butylphthalimide

and to investigate

chains

between the aromatic

of n and temperature_

they were bimolecuiar

have been

by XXII (n = 3 to 20) [34].

the ESR spectra

intramolecuiar

4 1353.

phthalimide

inorganic

and

on one end and the corresponding

end as illustrated

in turn,

as if

[31].

Finally,

the dynamic flexibility

that the shape of

which,

5-diketones

as measured by ESR spectroscopy

to investigate

the freqilency

moieties

processes

on the other

been deter;?ined

[32]_

on certain

diethyl

of certain anion

compounds

[33]_

transfer

a radical

of several

the oxanonatetraenyi

have been effected

chosen as a tool

and related

the sodium salts

adduct of a carboxamide

of dibenzo-18-crown-6 Electron

of carbanions

the sodium enolates

the ‘l-l NMRof

[30],

‘H ?c?R 01 an alkoxide

contain

NMRspectra

electron

transfer

radical

anion

in XXII where Ar =

[37]. Ar_CCHZ-fiArL XXII

The following

benzyl c39.

[38],

toluene

radical

401, mesitylene

radical

anion

[41],

radical

have been prepared

species

2.3-naphthobarrelane

phosphinyl)ethylene radical

anions

silyl-aniline5 RcfcrrncBp. :19

radical

1433,

phane derivatives

radical

[44], [45.

radical anions anions

and radical

46, 473.

anion [40].

[38,

39, 403.

several

of certain anions

e-

recorded:

benzene radical

2.3-naphthobarrelene

anion [41], [42],

ESR spectra

and their

radical

anion

anion

and trans-1.2-fi(diphenylhindered

triptycene

of a variety

alkylbiphenyl and [2.2]-paracyclo-

of ring

substituted

140 Ultraviolet

spectroscopy

evidence

for

tions

potassium

of

only

attributed this

carbanion

carbanion

or

kinetics

of

with

lithium

the bleached

papers

a variety

in this

solvent

methoxide

or of

the effect

of

though solu-

exhibited

the spectra

that state

the excited persisting

by the relative

spectra

from solutions

potassium

state

tightness

of

fluoradenide

ion pairs.

THF and dioxane

longer

the authors

Second,

the hydrogen of

area

of

spectroscopy

of N-sodioamino-N-heteroaromatics

in the amino forms

the presence

Specifically,

[48].

UV

on the

effected

behaved

by

differently

in THF than in dioxane. of

the aggregates

in

media.

spectroscopy;

that

ions,

direct

from disodiotetraphenylethylene

It was found

were rationalized

Two other

XXIV [SO]_

free

the first

suggested the presence of contact

photoejection

[49]_

the respective

exist

bonded,

to obtain

in this

been used to study

in the two solvents,

First,

fluoradenide

18-crown-6

electron

These results

in methanol

tetramethylamnonium

has also

a 530-nm pulse

pairing

to hydrogen

in the presence of spectroscopy

ion

has been employed

conclude like

microwave

exchange

base

that

XXIII,

proceeds

not in the tautomeric

via

between a a-ally1

brief

mention.

have been studied

in the crystalline

spectroscopy

reaction

deserve

state,

such comoounds

imino forms as

has been employed propylene

in

to demonstrate

and deuterated

intermediate

by infrared

DHSO in

[Sl].

0) i;+ I

XXIII

Concerning continued of

mechanistic

to be studied.

sodium biphenylide

determining

studies, The current

on cis-stilbene

step was the conversion

anion [52].

-_

-.

the isomerization investigation

where it of the cis-

of ewas centered

was determined

to trans-stilbene around

the use

that

the rate-

to the trans-stilbene

radical

141 TWO

papers

more

aromatic

with

radical

were reacted

anions -

with E-hexyl

clude

that the irreversible

state

with little

The second various

paper studied

etherealsolvents

to that

differences

in shapes of potassium,

P-chloroquinoline

anions

are described

reactions

with E-hexyl

These authors

radical

suggest

plots

enolates

XXV provided

of iodobenzene

Fragmentation

con-

transistion [53].

carried

that the negative

out in charge

of fluorides

rela-

paper discusses

the

in both papers.

are subjected

with this

and related

products

the authors

have been found to react

the reactions

Another paper concerned

and anthracene

fluoride

The latter described

halides

on the halide”

in such reactions anion.

alkyl

an early

delocaliration

the Arrhenius

chemistry [56].

“involves

and charge

but not lithium

[55].

similar

among others,

transfer

is more localized

to afford

photostimulation

thiolate

similar

of the naphthalene

Several

describes

electron

of certain

sodiumnaphthalene

bromide and chloride;

[54]-

state

the reaction

In the first,

bond breaking

in the ttansistion tive

describing

appeared

with

to

SRNl mechanism

compounds with certain

of intermediate

radical

anions

and rationalized.

xxv The term ERCl has been applied chain elimination

process

XXVI with XXVII to afford

to a unimolecular

as illustrated styrene

radical

anion-radical

by the light-stimulated

derivative

XXVIII [57].

Several

reaction

of

other

examples are included.

e-02N-C6H4

NO2

XXYI An alternative

mechanism for

the acyloin

condensation

has been presented

112 which

does not involve

sists

of

a series

of

a-diketones discrete

steps

XXIX-XXX1 illustrate

Structures

0"'

Instead,

[SS].

differing

only

?R'

three

?R'-

R-C-0-$R

the pathway proposed

one from the other of

the suggested

con-

by one electron_

intermediates.

; ?- ?' R-C=CR

R-C-O-CR 0-

xxx

XXIX

Reduction

of XXXII with potassium

C&S]_

These results

rather

than phenylated systems_

I

has been shown to afford

are in marked contrast

0

cyclononyl

xxx1

to similar

XXX11

which previously

Possible

mechanisms are

of

ketone

proposed

varying

depending

presumably

arise

cerned with the formation that species

like

for

of

have been reacted base

XXXIV

to give

of substrates

via aryne

intermediates.

of benzofurans

like

with several

products

upon choice

XXXIV are intermediates

hZ1n

the current

reaction.

Ph

enolates

in the presence

products

of alkylated

xxx111

chlorobenzenes

yields

XXX111

have been shown to afford

xxx11

A variety

reductions

FPh *_ ‘H

-

dianion

like

XXXVII where it

in their

*Z)n

xxxv

XXXIV-XXXVII

and base [60]. A second

formation

dialkylaminoin

Most of

the

paper was con-

is demonstrated [61].

; :

143

1,4-Rearrangement alkali

metals,

protonation. than

ion

has been

XXXVIII,

prepared

realized

[62].

1,2-rearrangements

could

not

from

to afford

and NMR spectroscopy

related

Evidence

of

and

be garnered

the

XXXIX

This

corresponding

as evidenced

1.4-migration

increases

to demonstrate

in

the

the

much less

Li<
presence

and

by carbonation,

is

order

chloride

of

facile CS.

non-classical

XL.

e-Ph-C6H4C(Ph)2(CH2)3M

Ph2!

(CH2)3C6H4-@‘h

XXXVIII

XXXIX Ph XL

Other of

the

studies

Stevens

and axial

Favorskii

reaction <

2.

SYNTHETIC ASPECTS A warning

about

organornetallic

chloryl safer

References

route.

p_ l-l9

deserve

include

mention

a quantitative

sigmatropic of

of

CIDNP study

pathways

in

3-(I;-haloacyl)indoles

certain

another

has been

dichlorinated

explosion

published

benzocyclobutene.

fluoride.

that

the

[66],

the mechanism

in

latter

the

[6S].

Favorskii

The desired

[69].

potassium

perchloryl

of and

[68].

fluoride

The current

explosion

t-butoxide.

n-butyllithium,

3-fluorobenzocyclobutene

base-

[67],

methylketones

involving

latter

reactions

2-bronobenzo[6,7]bicyclo[3_2_l]-act-6-en-3-one

the

of

[63].

and forbidden

rearrangements

equatorial

a mixture

rearrangements

rearrangement

1641 , allowed catalyzed

of

and an

occurred

has been

with

and perprepared

by a

c--

-

._--

..

-.

--

- - -_

144 Another described

strong

[70]

internal

to

propargyl butoxide group

potassium

and employed

terminal

(XLI.

the

XLII.

The reactions

that

are

of

facile

[70.

G = 0,

KOH to afford

R [72]_

in

acetylenes

compounds or

base,

contrathermodynamic

713.

N,

5)

XLIII,

3-aminopropylamide.

In another

have

been

or

XLIV

postulated

to

isomerization

study,

reacted

proceed

a variety

with

depending

has been

via

of

potassium

upon the diallene

of

base

-bis-

tand

the

intermediates.

= --R

xQ

XX

XLIV XL111

Metalation addition XLVI

of

(37%)

is

oxide

by trimethylsilypotassium

has been

found

to afford

followed

a mixture

of

by

XLV (28%)

and

[733.

synthesis

illustrated

3-methyl-l-butene

ethylene

Several their

of

new,

stable

being by the

cyclobutadienes

proton

abstraction

conversion

of

XLVII

have

been described.

by strong to XLVIII,

bases

[74].

the

last

step

The process

of

--

145

Double dehydrobromination addition C7S] -

of

dimethylamine

The authors

of

XLIX

has been

suggest

that

by potassium

found

the

to give

reaction

t-butoxide

followed

6-dimethylaminofulvene

proceeds

via

m-benzyne

by (L)

LI.

XLIX

Cyclopropane zation

of

disilazane

and cyclobutanone

chlorocyanohydrins Similar

[76].

aminocyanoepoxides

like

[77].

of

The subject

(n

= 2 or

cyclizations LIII

ring

Other cyclizations

781.

LII

cyanohydrins

have

to afford size

in

3)

such

been prepared by cycli-

have effected

been

by sodiohexamethyl-

carried

pyrrolidines

like

cyclizations

out

on certain

LIV

(G = NH, 0 or

H2)

has been discussed [77.

described in 1975 include the preparation of epoxides

from B-hydroxyalkylselenonium salts

[79] and of naphthyridines from dinitriles

[801-

PR Cl (CH2),CHCN

/

0

G

CN

Ar

Ar

ii

LII

4

LIII

LIV

Alkylation convenient

and subsequent

synthesis

of

oxidation

chain-extented

of

LV has been

and a-branched

found

a-amino

to constitute acids ; several

a

146

_

examples are listed

[81]. ‘:

(RS)2~=~-c~-~02c2bi5

LV Cyclobutanones tuents

are readily

systems like described

containing cleaved

LVI or LVII,

by basic

hydroxide,

[82,

(1luY) to afford

and methyllithium

to give

v-substituted

reductive

The nucleophiles

group.

substi-

In conjunction

831.

the method represents

of a carbonyl

a lkoxide,

or 3,x-trinethylenedithio

reagents

respectively

spiroannelations,

geminal alkylation

u,u-dibromo

acids,

with earlier

alkylation used to date

esters,

or include

and ketones.

respectively.

-sJ/-\,

( 4’ Other studies

in this

area that deserve

of LVIII with non-enolizable rt-ketosulfones

(LIX)

carbonyl-containing nucleophile

versus

carbonyl

0

to afford

the generation

functional

to a vinyl

cyclopropanes tives,

[84],

aldehydes

halide

epoxides

mention

include

the condensation

enol ethers

by conjugate

and a discussion

from the reactions

of the formation acid

of a of deriva-

compounds, and base [86].

X

SO2R”

M’

-._.,G ----Nu LX

LVIII

covered

LX (G =

addition

of a-haloacrylic

R

Several

of hypothetical

of Darzens intermediates

group or cyanide) [85],

CONU

papers discussed

included

aliphatic

semidiones.

bicyclo[3_2_0]hep-2-ene-6.7-semidiones

Systems specifically [87],

cycloheptane-1.2-

..

-emidiones certain

[88],

alkenyl

carbocyclic

Finally,

and cycloalkyl

conjugated

%

substituted

unsaturated

the preparations

have been described

3_

.. __,. ._-_. ._ .._

1,2-semidiones

1,2-semidiones

of saphthalene

cesiun

[89],

and

[90].

and phenylpyridine

cesium

[91].

REACTIONSNITH INORGANICAND ORGAhOMETALLIC COMPOlJiIDS Eight examples of complexes

of alkali

retal

hydrides

potassium

eXalilDle.

similarly,

this

and metallic examole,

hydride

no reaction

and LX11 have been observed

with certain

hydride

cation

LX:

magnesium alkyls

and di-c-butylnagnesium

and diphenylmagnesiun

are important

in

was observed

determining

and aryls

afford

give

[92].

For

LX1 in benzene;

LX11 in ether.

which

in the case of

in reactions

complex

!ithium

60th sol-rent

is

hydride

formed;

for

and dimethyl-

magnesium in ether. !4Mg2R4ti

YMgR2H LX1

A revieir discussing published

[93].

LXII

certain

The synthesis

aspects and crystal

(CSHS)2Ee2C2SbH8> has been described polyhedral

expansion

chloride.

Metallocarborane

been

synthesized

transistion

been

[95].

including

atoms migrate

several

corresponding

novel

to adjacent

nickelaboranes

Tetraborane the

halides

[94]_

of

certain

titanium, close

has also

has been anion

deprotonated

[99]_

Some of

discussed

[97,

by potassium

The preparation

and vanadium have

Gth

their

rearrangements

vertices

of

[96].

by a

and ferrous

the mixed-metal

polyhedral

polyhedral been

zirconium,

carboranes of

has been

of a new ferracarborane,

The compound was prepared

Four isomers

thermal

chemistry

sodium cyclopentadienide

with

complexes of

structure

(CsV5)2CoNiCB7H8 have been prepared_

presented

metal

4.5C2B7H9

by treatment

metal

carborane,

of

of metallocarborane

sodium,

then

bimetallochemistry in

has

which

The synthesis

the of

983. hydride B5H8-,

or

ammonia

to afford

B6Hg-,

B5H12-,

B6H11-;

148

and B7H12 are above

also

species

treatment alkene

Mixed

_

of [rOO].

aluminium

with

their

novet

to certain

t complexes

has been

area

of

metal

of

LX111

the

metal

metal [tO7],

of

reviews

anions,

of metal

of

this

species

analog

carbonyl

and with

has been alkylated

and

Thus.

such species

aromatics L-1143,

[112],

and methyl

from

the by

an

fialcoholates to give

of

with

its

in

published the

discusses Grignard have alkali

C8K [lOB]_

syntheses

reagents

metai

base NMR

of

[105].

effected

by

amalgams

Sodium-amalgam

IV halides

proton

concerned

disodium

been

species

with

LXIV

reduction

which

[109].

[IOS].

has

Reaction

has given recorded

of

anion [llO].

(csH,)MO(cO),(~~~~,)~

LX111

of

of

several

been

use

anions

and Group

(csH,)M~(c0)2(c~~~3)~l

Reactions

have

review

carbonyls

alkyl

presence

Finally,

for

yields

cyclopentadienide

new isonitrite-containing

by a variety

the

high

borabenzene

their

pentacarbonyl[methoxy(phenyl)carbene]chromium(O) LXV;

in

reported

[lOZ].

Another

alloy

in

sodium

compounds [tO4]_

has afforded

been alkylated

with

and with

sodium-potassium

synthesized

[l Ol] _

presented

compounds

corresponding

been

hydride

[103].

preparations

the

sodium

reacted

carbonyl

been

have

derivatives

as a transition

Convenient

of

been

patterns

tetracarbonylferrate

with

have

reactivity

organometallic

treatment

with

n-cyclopentadiene

the

have

A new route

chloride

corresponding In

trialkytboranes

diatkylbromoboranes

(borinato)cobal of

NMR and “B spectra

described.

LXIV

metal have

carbonyl been

anions

interacted

fluoroolefins organometallics

[113]. [115].

the

have

been

subject

with

a-chloroenamines

1.2,3-tri-&butylcyclopropenium

of

several

[111].

papers.

fluorocation

149 Carbonyl

ferrate

ferrates

have

bony1

aldehydes [lli’],

[116],

and to

With

with

sandwich

[122].

with

uranium

11241

sandwich

Finally, to

it

nickel,

with

reduce

THF has

Primary

involving

benzene

Alvarino.

been

silicon

substituted

cyclized

niobium

[125]

have

papers

prepared

from

LXVI

has been

[128].

by bases

in

the

l,l’-

to afford

been

Dipentadienylzinc and zinc

from additions

LXVII

of

and LXVIII

Chem_.

[127].

[129,

mono- and have

been

1301.

R2pCH2CH2PR2’ LXVIII

and H-B.

Schlegel,

J_ Organomet-

chloride

various

LXVII

H_ Guerra.

sodium

complexed

derivatives

RPHCH2CH2PH2

Pedulli.

of

chlorotriisopropylgermane

vinylphosphorus

like

The ability

has been enhanced by complexing

pentadienylpotassium

to certain

cyclooctatetraene

disclosed_

[126].

synthesized

negatively

with

mention.

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salts

Several

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LXVI

J-H_

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F. Bernardi. 6. 105 (1975) 711.

certain

de-

dipotassio-1,3,5,7-tetraphenylcycloocta-

stable

(i-C3H7)3GeNH2

2.

of

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phosphines

l_

stereospecific

[123].

disubstituted

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