Bimolecular Coupling in Olefin Metathesis: Correlating Structure and Decomposition for Leading and Emerging Ruthenium-Carbene Catalysts.

ABSTRACT: Bimolecular catalyst decomposition is a fundamental, long-standing challenge in olefin metathesis. Emerging ruthenium-cyclic(alkyl)(amino)carbene (CAAC) catalysts, which enable breakthrough advances in productivity and general robustness, are now known to be extraordinarily susceptible to this pathway. The details of the process, however, have hitherto been obscure. The present study provides the first detailed mechanistic insights into the steric and electronic factors that govern bimolecular decomposition. Described is a combined experimental and theoretical study that probes decomposition of the key active species, RuCl₂(L)(py)(═CH₂) 1 (in which L is the N-heterocyclic carbene (NHC) H₂IMes, or a CAAC ligand: the latter vary in the NAr group (NMes,

SUBMITTER: Nascimento DL 

PROVIDER: S-EPMC8397316 | biostudies-literature | 2021 Jul

REPOSITORIES: biostudies-literature