Cyclobutadiene platinum complex as a new type of precatalyst for hydrosilylation of alkenes and alkynes

Abstract

The readily available cyclobutadiene platinum complex [(C 4 Et 4 )PtCl 2 ] catalyzes hydrosilylation of alkenes and alkynes. The reaction typically proceeds at room temperature and does not require any solvent. The target products are obtained from both terminal and internal alkynes, as well as from terminal alkenes in 43-99% yields. The scope of silanes includes various tertiary silanes (Et 3 SiH, (EtO) 3 SiH, Ph 3 SiH) and the disubstituted silane Ph 2 SiH 2 . The hydrosilylation proceeds with typical anti-Markovnikov regioselectivity giving mainly β(E)-vinylsilanes from alkynes and linear alkyl silanes from alkenes.

Catalytic activity of cyclobutadiene rhodium complexes in hydrosilylation and other transformations of alkynes

“…17,18 Recently, we have shown that the cyclobutadiene platinum complex [Pt(C 4 Et 4 )Cl 2 ] can act as a hydrosilylation catalyst for alkenes and alkynes. 19 Therefore, we decided to test the activity of cyclobutadiene rhodium complexes [Rh(C 4 Et 4 )Hal] n (generated from 1 and Hal À ) as well as the related cyclooctadiene analog [Rh(cod)Cl] 2 in the model reaction of Et 3 SiH with 1-octyne (Table 1). It was reported that the cyclooctadiene complex [Rh(cod)Cl] 2 (at 1 mol% loading) converts the starting materials into a mixture of isomeric vinyl silanes 6, with Z-6 being the major product (70%).…”