Stability of difluorophosphines and their platinum complexes

32

122

STABILITY

OF DIFLUOROPHOSPHINES

AND THEIR

PLATINUM

COMPLEXES Lutz Hewr.

Peter G. Jones,

Reinhard

Schmutzler

Institut fiir Anorganische und Analytische Chemie der Technischen UniversitBt. Hagenring 30,330O Brunswick (F.R.G.) and Dietmar Schomburg Gesellschaft

ftir Biotechnologische Forschung mbH. Mascheroder Weg

1.

3300 Brunswick (F.R.G.) Lutz Heuera, Peter G,Jonesa, Dietmar lnstitut fir 3300

Anorganische

Braunschweig,

und Analytische Chemie der Technischen

Federal

Republic of

Forschung mbH, Mascheroder Compounds disproportionation.

Weg 1, 3300

Germany

e.g.:

2n RPF2

This type of reactions

compounds (R1.i) with PF2CI of preparing

(a);

Universitgt.

Gesellschaft

fijr

Hagenring 30,

Biotechnologische

Braunschweig. Federal Republic of Germany

involving carbon-bonded

X3P-F

are l/n

------Y

normally

(RPI,

+

unstable

because

of

(b).

redox

n RPF4.

is fairly slow if sterically demanding organic groups (e.g. tert.-

butyll or strongly electronegative

method

Schomburgb, and Reinhard Schmutzlera

groups (e.g.

CF3)

are

[ 1,2] C RLi + PF2CI -----+b

difluorophosphines

of the

used. The reaction

of organolithium

RPF2 + LiCl 1 therefore

type RPF2

(R = organic

provides a mild

substituent).

With

anthracyl lithium we observed the formation of anthracyl difluorophosphine, which dimerized

on

irradiation. The anthracyl difluorophosphine monomer and dimer are stable with respect to redox disproportionation and the dimer is also moderately air stable; it ‘was characterized diffraction

study. The partial hydrolysis of the PF2-group

by an X-ray

gave compounds of type RP(F)(OI(H).

In the case of R = 2,6_diphenoxyphenyl the corresponding fluorophosphonic acid was characterized by n.m.r.

spectra

and by an X-ray

Organodifluorophosphines

diffraction

reacted

study.

with cis-dichloro(~4-1,5-cyclooctadiene)platinum~II)

K2PtC14 to form cis-dichloro-bis(organodifluorophosphine)platinum(ll)

or

or tetrakis(organodifluoro-

phosphine)platinum(Ol. respectively. These complexes were chamterized

by n.m.r spectra and by

X-ray

involving PF2-groups,

diffraction

correlation

studies

for

R = But, Me5C5 [2].

between the Pt-P bond length and *J(PtF)

The tetrakis(aryldifluorophosphine)platinum(OI the PF2-group

complexes

borato))platinum(lI)

acidlplatinum(lll.

was found.

of bis(arylphosphonofluoridate)-bis

Bis{bis(2.5-dimethylphenylfluorophosphinito)-difluoro-

is the only product of the reaction of the appropriate {RPF(0)12Pt{RPF(OHI12

with BF3*Et20

and was characterized

1

L.Heuer and R.Schmutzler.

2

L.Heuer,

Dissertation,

J.Fluorine m

a

complexes were found to undergo hydrolysis of

and oxidation of the platinum with formation

(arylphosphonofluoridous

complex

For

by a single crystal X-ray diffraction s

(1988)

197.

Technische UniversitBt Braunschweig,

1989.

study.