Reaction with HSiMe

In Fig.l, two possible pathways to ft)-epoxy-fiinctionalized alkoxysilanes are displayed In case of route 1, the first step consists of the partial hydrosilylation of a,dienes with HSiMe Cl3 to give the corresponding ft>-alkenylchlorosilanes in 53-79 % yield. Although this reaction proceeds... 

The Chalk-Harrod type mechanism is proposed to be operative in the reaction of ethene with HSiMes, HSiEts and HSiPhs catalyzed by an early-late heterobimetallic complex, Cp2Ta(CH2)2lr(CO)2 . The proposed catalytic cycle is very similar to the one shown in Scheme 5, wherein [M] is Cp2Ta(CH2)2lr(CO), except for the dissociation of CO at the oxidative addition of HSiR3 and the coordination of CO at the reductive elimination of EtSiRs. This catalyst, however, only promotes the hydrosilylation of ethene, and higher alkenes are isomerized ". ... 

Cobalt carbonyl-catalyzed hydrosilylation of aromatic nitriles with HSiMes proceeds smoothly at 60 °C and ambient pressure of carbon monoxide in toluene to give N, Af-bis-TMS-amines 191 in moderate to excellent yields (equation 78) . Reactions of aliphatic nitriles require 100 °C, except for cyclopropanenitrile, to give 191 in 87-100% yields. The reaction of butanenitrile gives a mixture of 191 (R = n-Bu) (44%) and N, Af-bis-TMS-enanime CH3CH2CH=CHN(SiMe3)2 (20%). The reactions of a, yS-unsaturated nitriles bearing substituent(s) at the a- and/or -position(s) give N, Af-bis-TMS-enamines 192 (Z/E mixture) as the major products accompanied by iV, Af-bis-TMS-allylic amines 193 and/or saturated N, Af-bis-TMS-amines 194 (equation 19). ... 

The first example of an NHC-Fe catalyzed hydrosilylation reaction was reported by Peris et Piano-stool Fe complex 179, bearing a bidentate tyclo-pentadienyl-functionalized NHC ligand, displayed good activity in the hydrosilylation of aromatic aldehydes with HSiMe(OEt)2, although aliphatic aldehydes and ketones were not reduced under the same conditions (Figure 13.23). 

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