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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)

Springer Verlag

Manager: Ministerio de Economía y Competitividad (Espanya)
Author: Vummaleti, Sai Vikrama Chaitanya
Cavallo, Luigi
Poater Teixidor, Albert
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
Document access: http://hdl.handle.net/10256/13283
Language: eng
Publisher: Springer Verlag
Collection: info:eu-repo/semantics/altIdentifier/doi/10.1007/s00214-015-1622-x
info:eu-repo/semantics/altIdentifier/issn/1432-881X
info:eu-repo/semantics/altIdentifier/eissn/1432-2234
info:eu-repo/grantAgreement/MICINN//RYC-2009-05226/ES/RYC-2009-05226/
info:eu-repo/grantAgreement/EC/FP7/293900/EU/Ab initio Statics and Molecular Dynamics Simulation of Olefin Metathesis Catalysts for pharmacological purposes/COMPUTEDRUG
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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