Cerium‐Catalyzed Hydrosilylation of Acrylates to Give α‐Silyl Esters

The homoleptic organocerium complex Ce{C(SiHMe2)3}3 (1) reacts with B(C6F5)3 to produce the zwitterionic bis(alkyl) hydridoborato Ce{C(SiHMe2)3}2HB(C6F5)3 (2). NMR and IR spectroscopy and X‐ray crystallography indicate that each alkyl ligand contains two bridging Ce↼H‐Si interactions in both 1 and 2. Compound 2 serves as a precatalyst for the hydrosilylation of acrylates to give α‐silyl esters at room temperature with a turnover number of 2200. Zwitter: A zwitterionic organocerium hydridoborato complex is highly active for the catalytic addition of acrylates and secondary silanes to give α‐silyl esters. The ester functionality is not reduced under these reaction conditions despite the oxophilicity of the cerium catalyst. NMR and IR spectroscopy and X‐ray crystallography indicate that each alkyl ligand forms two bridging Ce↼H‐Si interactions. TOF=turnover frequency, and TON=turnover number.