Synthesis and Activity of Vanadium Oxo NHC Alkylidenes. Remarkable Preference for Degenerate Metathesis and Application for Carbon Isotope Exchange
Belov, Dmitry S. (Florida International University. Department of Chemistry and Biochemistry)
Acosta, Carlos M. (Florida International University. Department of Chemistry and Biochemistry)
Garcia-Molina, Miquel (Universitat Autònoma de Barcelona. Departament de Química)
Rue, Kelly L. (Florida International University. Department of Chemistry and Biochemistry)
Solans Monfort, Xavier (Universitat Autònoma de Barcelona. Departament de Química)
Bukhryakov, Konstantin V. (Florida International University. Department of Chemistry and Biochemistry)

Date:	2022
Abstract:	V imido NHC phosphine alkylidenes are the most efficient V catalysts for ring-closing olefin metathesis of various terminal dienes. The presence of imido and phosphine ligands is responsible for catalyst decomposition. Therefore, the development of phosphine-free V oxo NHC alkylidenes is a logical next step to further improve V-based olefin metathesis. Herein we report V oxo NHC chloride and alkoxide alkylidenes and their reactivity in olefin metathesis. V oxo NHC chloride is readily involved in cycloaddition/cycloreversion steps with olefins. However, a remarkable preference for the formation of a 1,3-metallacyclobutane (MCB) leads to exclusive methylene group exchange (degenerate metathesis) utilized for carbon isotope exchange. DFT studies further support the preference for the 1,3-MCB formation.
Grants:	Agencia Estatal de Investigación PID2020-112715GB-I00 Agència de Gestió d'Ajuts Universitaris i de Recerca 2017/SGR-1323
Rights:	Tots els drets reservats.
Language:	Anglès
Document:	Article ; recerca ; Versió acceptada per publicar
Published in:	Organometallics, Vol. 41, Issue 21 (November 2022) , p. 2897-2902, ISSN 1520-6041

DOI: 10.1021/acs.organomet.2c00465

Postprint 7 p, 1.1 MB

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