The driving force role of ruthenacyclobutanes

Sai V. C. Vummaleti; Luigi Cavallo; Albert Poater

doi:10.1007/s00214-015-1622-x

The driving force role of ruthenacyclobutanes

Sai V. C. Vummaleti, Luigi Cavallo, Albert Poater

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9 Scopus citations

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.

Original language	English (US)
Journal	Theoretical Chemistry Accounts
Volume	134
Issue number	3
DOIs	https://doi.org/10.1007/s00214-015-1622-x https://doi.org/10.1007/978-3-662-49221-5_11
State	Published - Feb 7 2015

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: 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).

ASJC Scopus subject areas

Physical and Theoretical Chemistry

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title = "The driving force role of ruthenacyclobutanes",

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.",

author = "Vummaleti, {Sai V. C.} and Luigi Cavallo and Albert Poater",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: 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).",

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doi = "10.1007/s00214-015-1622-x",

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T1 - The driving force role of ruthenacyclobutanes

AU - Vummaleti, Sai V. C.

AU - Cavallo, Luigi

AU - Poater, Albert

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: 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).

PY - 2015/2/7

Y1 - 2015/2/7

N2 - 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.

AB - 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.

UR - http://hdl.handle.net/10754/564049

UR - http://link.springer.com/10.1007/s00214-015-1622-x

UR - http://www.scopus.com/inward/record.url?scp=84922347931&partnerID=8YFLogxK

U2 - 10.1007/s00214-015-1622-x

DO - 10.1007/s00214-015-1622-x

M3 - Article

SN - 1432-881X

VL - 134

JO - Theoretical Chemistry Accounts

JF - Theoretical Chemistry Accounts

IS - 3

ER -

The driving force role of ruthenacyclobutanes

Abstract

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