Four-Coordinated Manganese(II) Disilyl Complexes for the Hydrosilylation of Aldehydes and Ketones with 1,1,3,3-Tetramethyldisiloxane

摘要

The coordinatively unsaturated manganase(II) bis(supersilyl) complex Mn[Si(SiMe3)(3)](2)(THF)(2) (2) was synthesized in one step via the reaction of MnBr2 with two equivalents of KSi(SiMe3)(3) in THF. Complex 2 acts as an effective precatalyst for the catalytic hydrosilylation of aldehydes and ketones with 1,1,3,3-tetramethyldisiloxane (TMDS). The catalytic efficiency can be improved by combining 2 and adamantyl isocyanide (CNAd). The stoichiometric reaction of 2 and two equivalents of CNAd led to the isolation of Mn[Si(SiMe3)(3)](2)(CNAd)(2) (3) in high yield. Complex 3 shows superior catalytic performance than 2 in the hydrosilylation of relatively unreactive ketones.