Mechanistic Insights of a Selective C-H Alkylation of Alkenes by a Ru–based Catalyst and Alcohols

摘要: Density functional theory calculations have been used to investigate the reaction mechanism for [(C6H6)(PCy3)(CO)RuH]+ (1; Cy, cyclohexyl) mediated alkylation of indene substrate using ethanol as solvent. According Yi et al. [Science 2011, 333, 1613] plausible involves a cationic Ru-alkenyl species, which is initially formed from 1 with two equivalents olefin via vinylic C−H activation and an alkane elimination step. Once active catalytic species achieved oxidative addition step faced. The latter together next C−C bond formation might display upper barrier cycle. Having these experimental insights at hand, we investigated in detail whole pathway several computational DFT approaches including alternative pathways, higher energy.