Reaction of octacarbonyldicobalt with organo-silanes, -germanes, and -stannanes: formation, properties, and vibrational spectra of trimethylgermyltetracarbonylcobalt and related complexes
- 1 January 1974
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 3,p. 264-269
- https://doi.org/10.1039/dt9740000264
Abstract
The hydrides R3MH (R = Me, M = Si, Ge, or Sn; R = Et, M = Ge) react exothermically with Co2(CO)8 at 20 °C affording in high yield the complexes R3MCo(CO)4[R = Me, M = Si (I); M = Ge (II); M = Sn (III); and R = Et, M = Ge (IV)]. Conversion of (I) to (II) or (III) and of (II) to (III) occurs on reaction with Me3MH (M = Ge or Sn), and (II) can also be prepared from (I) with Me3GeBr. The Ge–Co bond in (II) is cleaved by HCl or HgCl2; (II) with Et3N or piperidine forms tetracarbonylcobaltate adducts. The vibrational spectra of (II)–(IV) are reported, with ν(M–Co) assigned to polarised Raman shifts respectively at 192,177, and 188 cm–1. Variation with M of the vapour-phase i.r.-intensity of one of the two a1 CO stretching fundamentals expected for C3v symmetry points to a significant out-of-plane displacement of equatorial carbonyl groups in the direction of the silicon atom in (I), but with no analogous effect in (II) or (III). Deviations from C3v selection rules observed in the solid state for (II) and (III) are also discussed.Keywords
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