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

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 to Yi et al. [Science 2011, 333, 1613] the plausible reaction mechanism involves a cationic Rualkenyl 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

A.P. thanks the Spanish MINECO for a project CTQ2014-59832-JIN

Wiley

Director: Ministerio de Economía y Competitividad (Espanya)
Autor: Poater Teixidor, Albert
Vummaleti, Sai Vikrama Chaitanya
Polo Ortiz, Alfonso
Cavallo, Luigi
Resum: 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 to Yi et al. [Science 2011, 333, 1613] the plausible reaction mechanism involves a cationic Rualkenyl 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
A.P. thanks the Spanish MINECO for a project CTQ2014-59832-JIN
Accés al document: http://hdl.handle.net/2072/298903
Llenguatge: eng
Editor: Wiley
Drets: Tots els drets reservats
Matèria: Funcional de densitat, Teoria del
Density functionals
Catalitzadors de rodi
Rhodium catalyst
Alquilació
Alkylation
Títol: Mechanistic Insights of a Selective C-H Alkylation of Alkenes by a Ru–based Catalyst and Alcohols
Tipus: info:eu-repo/semantics/article
Repositori: Recercat

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