90148-96-2Relevant academic research and scientific papers
Stereochemistry of the insertion of manganese into Si-H and Ge-H bonds. Complexes containing a two-electron, three-center Mn?H?Si (or Ge) interaction
Carré, Francis,Colomer, Ernesto,Corriu, Robert J. P.,Vioux, André
, p. 1272 - 1278 (2008/10/08)
A crystallographic study of the complex (-)-(η5-CH3C5H4)(CO) 2(1-NpPhMeSi)(H)Mn (1,1-Np = 1-C10H7, Ph = C6H5, Me = CH3) reveals that the oxidative addition of (+)-1-NpPhMeSiH on methylcymantrene takes place with retention of configuration at silicon. The gennyl complexes (η5CH3C5H4)(CO) 2(R3Ge)(H)Mn are prepared either by oxidative addition of R3GeH (R = Ph) on (η5-CH3C5H4)(CO)3Mn or by protonation of the related anions [(η5-CH3C5H4)(CO) 2(R3Ge)Mn]- (R3 = Ph3, 1-NpPhMe, Cl3). Only the cis isomers are obtained. Complex 2 (R = Ph) exhibits a higher acidity than the silyl analogue. This acidity is close to that of HCl. However both 1 and 2 undergo easy elimination of R3SiH or R3GeH when treated with PPh3. The Mn-Ge bond is cleaved by H2O, CH3OH, Cl2, and CCl4; this behavior contrasts with that of 1 since Cl2 or CCl4 lead to elimination. These observations are in agreement with a two-electron, three-center bond between manganese, silicon (or germanium), and hydrogen.
