The mechanism of oxidative addition of Pd(0) to Si-H bonds: electronic effects, reaction mechanism, and hydrosilylation.

ABSTRACT: The oxidative addition of Pd to Si-H bonds is a crucial step in a variety of catalytic applications, and many aspects of this reaction are poorly understood. One important yet underexplored aspect is the electronic effect of silane substituents on reactivity. Herein we describe a systematic investigation of the formation of silyl palladium hydride complexes as a function of silane identity, focusing on electronic influence of the silanes. Using [(μ-dcpe)Pd]₂ (dcpe = dicyclohexyl(phosphino)ethane) and tertiary silanes, data show that equilibrium strongly favours products formed from electron-deficient silanes, and is fully dynamic with respect to both temperature and product distribution. A notable kinetic isotope effect (KIE) of 1.21 is observed with H/DSiPhMe₂ at 233

SUBMITTER: Hurst MR 

PROVIDER: S-EPMC8513848 | biostudies-literature | 2021 Oct

REPOSITORIES: biostudies-literature