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Catalysts 2017, 7(12), 389; doi:10.3390/catal7120389

In Silico Switch from Second- to First-Row Transition Metals in Olefin Metathesis: From Ru to Fe and from Rh to Co

Institut de Química Computacional i Catàlisi and Departament de Química, Universitat de Girona, Campus Montilivi, 17003 Girona, Spain
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Received: 20 November 2017 / Revised: 9 December 2017 / Accepted: 11 December 2017 / Published: 14 December 2017
(This article belongs to the Special Issue Catalysis of Olefin Metathesis)
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Abstract

Density functional theory (DFT) calculations have been used to investigate the behavior of different transition metals from Groups 8 (Fe and Ru) and 9 (Co and Rh) in an already well-known catalytic mechanism, which is based on an Ru(SIMes)(PPh3)Cl2=CH(Ph) complex. As expected, Ru has proven to perform better than their Fe, Co, and Rh counterparts. Even though the topographic steric maps analysis shows no difference in sterical hindrance for any of the metal centers, geometrically, the Fe-based species show a high rigidity with shorter and stronger bonds confirmed by Mayer Bond Orders. The systems bearing Co as a metallic center might present a reactivity that is, surprisingly, too high according to conceptual DFT, which would consequently be a drawback for the formation of the fundamental species of the reaction pathway: the metallacycle intermediate. View Full-Text
Keywords: cobalt; ruthenium; rhodium; density functional theory; olefin metathesis; iron; reaction mechanism; N-heterocyclic carbene; catalysis cobalt; ruthenium; rhodium; density functional theory; olefin metathesis; iron; reaction mechanism; N-heterocyclic carbene; catalysis
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Luque-Urrutia, J.A.; Gimferrer, M.; Casals-Cruañas, È.; Poater, A. In Silico Switch from Second- to First-Row Transition Metals in Olefin Metathesis: From Ru to Fe and from Rh to Co. Catalysts 2017, 7, 389.

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