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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

© ChemistrySelect, 2016, vol. 1, núm. 14, p. 4218 - 4228

Wiley

Author: Poater Teixidor, Albert
Vummaleti, Sai Vikrama Chaitanya
Polo Ortiz, Alfonso
Cavallo, Luigi
Date: 2016
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
Format: application/pdf
ISSN: 2365-6549
Document access: http://hdl.handle.net/10256/13488
Language: eng
Publisher: Wiley
Collection: MINECO/PE 2015-2018/CTQ2014-59832-JIN
Reproducció digital del document publicat a: http://dx.doi.org/10.1002/slct.201600860
Articles publicats (D-Q)
Is part of: © ChemistrySelect, 2016, vol. 1, núm. 14, p. 4218 - 4228
Rights: Tots els drets reservats
Subject: Funcional de densitat, Teoria del
Density functionals
Catalitzadors de rodi
Rhodium catalyst
Alquilació
Alkylation
Title: Mechanistic Insights of a Selective C-H Alkylation of Alkenes by a Ru–based Catalyst and Alcohols
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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