Mechanism of the cooperative Si-H bond activation at Ru-S bonds.

ABSTRACT: The nature of the hydrosilane activation mediated by ruthenium(ii) thiolate complexes of type [(R₃P)Ru(SDmp)]⁺[BAr^F₄]^- is elucidated by an in-depth experimental and theoretical study. The combination of various ruthenium(ii) thiolate complexes and tertiary hydrosilanes under variation of the phosphine ligand and the substitution pattern at the silicon atom is investigated, providing detailed insight into the activation mode. The mechanism of action involves reversible heterolytic splitting of the Si-H bond across the polar Ru-S bond without changing the oxidation state of the metal, generating a ruthenium(ii) hydride and sulfur-stabilized silicon cations, i.e. metallasilylsulfonium ions. These stable yet highly reactive adducts,

SUBMITTER: Stahl T 

PROVIDER: S-EPMC5707498 | biostudies-literature | 2015 Jul

REPOSITORIES: biostudies-literature