The driving force role of ruthenacyclobutanes

Handle URI:
http://hdl.handle.net/10754/564049
Title:
The driving force role of ruthenacyclobutanes
Authors:
Vummaleti, Sai V. C. ( 0000-0001-7276-2475 ) ; Cavallo, Luigi ( 0000-0002-1398-338X ) ; Poater, 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.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division; Chemical Science Program
Publisher:
Springer Nature
Journal:
Theoretical Chemistry Accounts
Issue Date:
7-Feb-2015
DOI:
10.1007/s00214-015-1622-x
Type:
Article
ISSN:
1432881X
Sponsors:
A.P. thanks the Spanish MINECO for a Ramon y Cajal contract (RYC-2009-05226) and a Jose Castillejo fellowship (CAS14/00165), and European Commission for a Career Integration Grant (CIG09-GA-2011-293900).
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorVummaleti, Sai V. C.en
dc.contributor.authorCavallo, Luigien
dc.contributor.authorPoater, Alberten
dc.date.accessioned2015-08-03T12:29:49Zen
dc.date.available2015-08-03T12:29:49Zen
dc.date.issued2015-02-07en
dc.identifier.issn1432881Xen
dc.identifier.doi10.1007/s00214-015-1622-xen
dc.identifier.urihttp://hdl.handle.net/10754/564049en
dc.description.abstractDFT 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.en
dc.description.sponsorshipA.P. thanks the Spanish MINECO for a Ramon y Cajal contract (RYC-2009-05226) and a Jose Castillejo fellowship (CAS14/00165), and European Commission for a Career Integration Grant (CIG09-GA-2011-293900).en
dc.publisherSpringer Natureen
dc.subjectDFT calculationsen
dc.subjectMetallacycleen
dc.subjectOlefin metathesisen
dc.subjectRuthenacyclobutaneen
dc.subjectRutheniumen
dc.titleThe driving force role of ruthenacyclobutanesen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentChemical Science Programen
dc.identifier.journalTheoretical Chemistry Accountsen
dc.contributor.institutionInstitut de Química Computacional i Catàlisi and Departament de Química, Universitat de Girona, Campus MontiliviGirona, Catalonia, Spainen
kaust.authorVummaleti, Sai V. C.en
kaust.authorCavallo, Luigien
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