Hydrosilylation of Aldehydes and Ketones Catalysed by Bis(phosphinite) Pincer Platinum Hydride Complexes

Abstract

Abstract Bis(phosphinite) pincer platinum hydride complexes, [2,6‐(R 2 PO) 2 C 6 H 3 ]PtH (R= t Bu, i Pr), were synthesized, characterized and applied to the hydrosilylation of aldehydes and ketones. NMR study and single crystal X‐ray diffraction analysis indicated that the hydrides in these two platinum complexes are comparatively less hydridic: down‐field 1 H NMR resonances (0.71 and 0.98 ppm) and weak Pt−H interactions were observed. Both the platinum complexes were found to be good catalysts for the hydrosilylation of aldehydes and ketones with phenylsilane. The corresponding alcohols were isolated in good to excellent yields following basic hydrolysis of the resultant hydrosilylation products and turnover frequencies (TOFs) up to 3200 h −1 were achieved at 60 °C in toluene, which are much higher than those of the hydrosilylation catalysed by the corresponding nickel pincer hydride complexes. A possible mechanism for the present hydrosilylation process was discussed. magnified image