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The driving force role of ruthenacyclobutanes

DFT calculations have been used to determine the thermodynamic and kinetic preference for ruthenacyclobutanes resulting from the experimentally proposed interconversion pathways (olefin and alkylidene rotations) through the investigation of cross-metathesis reaction mechanism for neutral Grubbs catalyst, RuCl2(=CHEt)NHC (A), with ethylene and 1-butene as the substrates. Our results show that although the proposed interconversions are feasible due to the predicted low energy barriers (2-6 kcal/mol), the formation of ruthenacyclobutane is kinetically favored over the competitive reactions involving alkylidene rotations. In comparison with catalyst A, the reaction energy profile for cationic Piers catalyst [RuCl2(=CHPCy3)NHC+] (B) is more endothermic in nature with both ethylene and 1-butene substrates

A.P. thanks the Spanish MINECO for a Ramón y Cajal contract (RYC-2009-05226) and a José Castillejo fellowship (CAS14/00165), and European Commission for a Career Integration Grant (CIG09-GA-2011-293900)

© Theoretical Chemistry Accounts, 2015, vol. 134, núm 22

Springer Verlag

Author: Vummaleti, Sai Vikrama Chaitanya
Cavallo, Luigi
Poater Teixidor, Albert
Date: 2015 March
Abstract: DFT calculations have been used to determine the thermodynamic and kinetic preference for ruthenacyclobutanes resulting from the experimentally proposed interconversion pathways (olefin and alkylidene rotations) through the investigation of cross-metathesis reaction mechanism for neutral Grubbs catalyst, RuCl2(=CHEt)NHC (A), with ethylene and 1-butene as the substrates. Our results show that although the proposed interconversions are feasible due to the predicted low energy barriers (2-6 kcal/mol), the formation of ruthenacyclobutane is kinetically favored over the competitive reactions involving alkylidene rotations. In comparison with catalyst A, the reaction energy profile for cationic Piers catalyst [RuCl2(=CHPCy3)NHC+] (B) is more endothermic in nature with both ethylene and 1-butene substrates
A.P. thanks the Spanish MINECO for a Ramón y Cajal contract (RYC-2009-05226) and a José Castillejo fellowship (CAS14/00165), and European Commission for a Career Integration Grant (CIG09-GA-2011-293900)
Format: application/pdf
ISSN: 1432-881X (versió paper)
1432-2234 (versió electrònica)
Document access: http://hdl.handle.net/10256/13283
Language: eng
Publisher: Springer Verlag
Collection: MINECO/PN 2012-2015/RYC-2009-05226
Reproducció digital del document publicat a: http://dx.doi.org/10.1007/s00214-015-1622-x
Articles publicats (D-Q)
info:eu-repo/grantAgreement/EC/FP7/293900
Is part of: © Theoretical Chemistry Accounts, 2015, vol. 134, núm 22
Rights: Tots els drets reservats
Subject: Funcional de densitat, Teoria del
Density functionals
Metàtesi (Química)
Metathesis (Chemistry)
Ruteni
Ruthenium
Title: The driving force role of ruthenacyclobutanes
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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