Item


Mechanistic Insights of a Selective C-H Alkylation of Alkenes by a Ru鈥揵ased 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

Manager: Ministerio de Econom铆a y Competitividad (Espanya)
Author: Poater Teixidor, Albert
Vummaleti, Sai Vikrama Chaitanya
Polo Ortiz, Alfonso
Cavallo, Luigi
Abstract: 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
Document access: http://hdl.handle.net/2072/298903
Language: eng
Publisher: Wiley
Rights: Tots els drets reservats
Subject: Funcional de densitat, Teoria del
Density functionals
Catalitzadors de rodi
Rhodium catalyst
Alquilaci贸
Alkylation
Title: Mechanistic Insights of a Selective C-H Alkylation of Alkenes by a Ru鈥揵ased Catalyst and Alcohols
Type: info:eu-repo/semantics/article
Repository: Recercat

Subjects

Authors