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| Ministerio de EconomÃa y Competitividad (Espanya) | |
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Vummaleti, Sai Vikrama Chaitanya
Cavallo, Luigi Poater Teixidor, Albert |
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| 2015 March | |
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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) |
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| application/pdf | |
| http://hdl.handle.net/10256/13283 | |
| eng | |
| Springer Verlag | |
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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 |
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| Tots els drets reservats | |
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Funcional de densitat, Teoria del
Density functionals Metà tesi (QuÃmica) Metathesis (Chemistry) Ruteni Ruthenium |
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| The driving force role of ruthenacyclobutanes | |
| info:eu-repo/semantics/article | |
| DUGiDocs |
