synthesis of compounds containing the ge-co bond

SYNTHESIS OF COMPOUNDS CONTAINING THE

A. N. Nesraeyanov, K. N. Anisimov, N. E. Kolobova, and V. N. Khandozhko

G e - C o B O N D

UDC 542.91+547.1' 3

We have found that dieobalt octacarbonyl reacts with germanium tetrachloride in tetrahydrofuran (THF) according to the equation

o 20

3Coz (CO)8 + 2GeCh --~ 2CI~Go [Co (CO}~]z + 2CoCIz + 8C0 (t)

Compound (I), i so l a t ed with an a lmos t s t o i e h i o m e t r i e y i e ld , r e a c t s with t r iphenylph~sphine in n - h e x - ane at r oom t e m p e r a t u r e giving the complex (II)

Cl~Ge [Co(CO) ~]z + PPh~ -+ ChGe [Co(CO) 4][CO(CO) ~PPh~] + CO (II)

In boiling n 'hexane, triphenylphosphine takes part in an exchange reaction with two of the carbonyl groups of the complex (I)

C12Ge [Co(CO) ~]~ + 2PPh~ ~ ClzGe [Co(CO) aPPhs]z "q'- 2C0 (III)

Compound (lid can be obtained at room temperature by the action of triphenylphosphine on (I) in tetrahydrofuran.

The compounds obtained were identified by elementary analysis and IR spectra, the results of which, together with the melting points and yields, are given in Table 1.

TABLE i ]

corn- I nap, ~ pound

I

(II)(I) 1105 106

(Il l)

yield,~ t

93

91

97

Found, %

t9,79

41.85

52.64

H a l

14,58

Calculated,%

C Hal

19.75 14.61

41.67

52.83

(CO) *

2117, 2098, 2058 2035, 2020. 2106, 2056, 2029 2018, 1994, 1980 2a50, 2030, I986 1970, 1960.

*The IR spectra were taken in THF. UR-10 instrument.

Ins t i tu te of H e t e r o o r g a n i c Compounds, Academy of Sc iences of the USSR. T r a n s l a t e d f rom Izves t iya Akademii Nauk SSSR, Se r iya Kh imicheskaya , No. 8, pp. 1879-1880, August , 1967. Or ig ina l a r t i c l e submi t ted May 22, 1967.

1812