TY - JOUR
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 -