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Mechanistic Insights of a Selective C‐H Alkylation of Alkenes by a Ru–based Catalyst and Alcohols
Author(s) -
Poater Albert,
Vummaleti Sai Vikrama Chaitanya,
Polo Alfonso,
Cavallo Luigi
Publication year - 2016
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201600860
Subject(s) - chemistry , catalysis , olefin fiber , alkylation , catalytic cycle , density functional theory , alkane , substrate (aquarium) , indene , reaction mechanism , cationic polymerization , medicinal chemistry , computational chemistry , combinatorial chemistry , organic chemistry , oceanography , geology
Density functional theory calculations have been used to investigate the reaction mechanism for [(C 6 H 6 )(PCy 3 )(CO)RuH] + ( 1 ; Cy, cyclohexyl) mediated alkylation of indene substrate using ethanol as solvent. According to Yi et al. [ Science 2011 , 333 , 1613] the plausible reaction mechanism involves a cationic Ru‐alkenyl species, which is initially formed from 1 with two equivalents of the olefin substrate via the vinylic C−H activation and an alkane elimination step. Once the active catalytic species is achieved the oxidative addition step is faced. The latter step together with the next C−C bond formation might display the upper barrier of the catalytic cycle. Having these experimental insights at hand, we investigated in detail the whole reaction pathway using several computational DFT approaches including alternative pathways, higher in energy.