caa a22 4500 605487723 CHVBK 20210128100452.0 cr unu---uuuuu 210128e20150301xx s 000 0 eng 10.1007/s00214-015-1622-x doi (NATIONALLICENCE)springer-10.1007/s00214-015-1622-x The driving force role of ruthenacyclobutanes [Elektronische Daten] [Sai Vummaleti, Luigi Cavallo, Albert Poater] 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 (2-6kcal/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. Springer-Verlag Berlin Heidelberg, 2015 Olefin metathesis nationallicence Metallacycle nationallicence Ruthenium nationallicence Ruthenacyclobutane nationallicence DFT calculations nationallicence SIMes : 1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazolin-2-ylidene nationallicence DMDAM : Dimethyl diallyl malonate nationallicence Vummaleti Sai Physical Sciences and Engineering Division, Kaust Catalysis Center, King Abdullah University of Science and Technology, 23955-6900, Thuwal, Saudi Arabia aut Cavallo Luigi Physical Sciences and Engineering Division, Kaust Catalysis Center, King Abdullah University of Science and Technology, 23955-6900, Thuwal, Saudi Arabia aut Poater Albert Institut de Química Computacional i Catàlisi and Departament de Química, Universitat de Girona, Campus Montilivi, 17071, Girona, Catalonia, Spain aut Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/3(2015-03-01), 1-6 1432-881X 134:3<1 2015 134 214 https://doi.org/10.1007/s00214-015-1622-x text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00214-015-1622-x text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Vummaleti Sai Physical Sciences and Engineering Division, Kaust Catalysis Center, King Abdullah University of Science and Technology, 23955-6900, Thuwal, Saudi Arabia aut NATIONALLICENCE 700 1- Cavallo Luigi Physical Sciences and Engineering Division, Kaust Catalysis Center, King Abdullah University of Science and Technology, 23955-6900, Thuwal, Saudi Arabia aut NATIONALLICENCE 700 1- Poater Albert Institut de Química Computacional i Catàlisi and Departament de Química, Universitat de Girona, Campus Montilivi, 17071, Girona, Catalonia, Spain aut NATIONALLICENCE 773 0- Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/3(2015-03-01), 1-6 1432-881X 134:3<1 2015 134 214