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

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

A.P. thanks the Spanish MINECO for a project CTQ2014-59832-JIN and Xarxa de Química Teòrica i Computacional for a VALCHEM2016 project

MDPI (Multidisciplinary Digital Publishing Institute)

Manager: Ministerio de Economía y Competitividad (Espanya)
Author: Luque Urrutia, Jesús Antonio
Gimferrer Andrés, Martí
Casals Cruañas, Èric
Poater Teixidor, Albert
Date: 2017 December 14
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
A.P. thanks the Spanish MINECO for a project CTQ2014-59832-JIN and Xarxa de Química Teòrica i Computacional for a VALCHEM2016 project
Format: application/pdf
Document access: http://hdl.handle.net/10256/14769
Language: eng
Publisher: MDPI (Multidisciplinary Digital Publishing Institute)
Collection: info:eu-repo/semantics/altIdentifier/doi/10.3390/catal7120389
info:eu-repo/semantics/altIdentifier/eissn/2073-4344
info:eu-repo/grantAgreement/MINECO//CTQ2014-59832-JIN/ES/ESCANEO COMPUTACIONAL DE RELACIONES ESTRUCTURA%2FACTIVIDAD DE CATALIZADORES DE OXIDACION DEL AGUA PARA LA GENERACION DE H2/
Rights: Attribution 4.0 Spain
Rights URI: http://creativecommons.org/licenses/by/4.0/es/
Subject: Funcional de densitat, Teoria del
Density functionals
Mecanismes de reacció (Química)
Reaction mechanisms (Chemistry)
Metàtesi (Química)
Metathesis (Chemistry)
Alquens
Alkenes
Title: In Silico Switch from Second- to First-Row Transition Metals in Olefin Metathesis: From Ru to Fe and from Rh to Co
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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