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

The coordinatively unsaturated manganase(II) bis(supersilyl) complex Mn[Si(SiMe 3 ) 3 ] 2 (THF) 2 ( 2 ) was synthesized in one step via the reaction of MnBr 2 with two equivalents of KSi(SiMe 3 ) 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(SiMe 3 ) 3 ] 2 (CNAd) 2 ( 3 ) in high yield. Complex 3 shows superior catalytic performance than 2 in the hydrosilylation of relatively unreactive ketones.