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Versatile deprotonated NHC: C,N-bridged dinuclear iridium and rhodium complexes

Bearing the versatility of N-heterocyclic carbene (NHC) ligands, here density functional theory (DFT) calculations unravel the capacity of coordination of a deprotonated NHC ligand (pNHC) to generate a doubly C2,N3-bridged dinuclear complex. Here, in particular the discussion is based on the combination of the deprotonated 1-arylimidazol (aryl = mesityl (Mes)) with [M(cod)(μ-Cl)] (M = Ir, Rh) generated two geometrical isomers of complex [M(cod){µ-C3H2N2(Mes)-κC2,κN3}]2). The latter two isomers display conformations head-to-head (H-H) and head-to-tail (H-T) of CS and C2 symmetry, respectively. The isomerization from the H-H to the H-T conformation is feasible, whereas next substitutions of the cod ligand by CO first, and PMe3 later confirm the H-T coordination as the thermodynamically preferred. It is envisaged the exchange of the metal, from iridium to rhodium, confirming here the innocence of the nature of the metal for such arrangements of the bridging ligands

A.P. thanks the Spanish MINECO for a project CTQ2014-59832-JIN

Beilstein-Institut

Director: Ministerio de Economía y Competitividad (Espanya)
Autor: Poater Teixidor, Albert
Data: 22 gener 2016
Resum: Bearing the versatility of N-heterocyclic carbene (NHC) ligands, here density functional theory (DFT) calculations unravel the capacity of coordination of a deprotonated NHC ligand (pNHC) to generate a doubly C2,N3-bridged dinuclear complex. Here, in particular the discussion is based on the combination of the deprotonated 1-arylimidazol (aryl = mesityl (Mes)) with [M(cod)(μ-Cl)] (M = Ir, Rh) generated two geometrical isomers of complex [M(cod){µ-C3H2N2(Mes)-κC2,κN3}]2). The latter two isomers display conformations head-to-head (H-H) and head-to-tail (H-T) of CS and C2 symmetry, respectively. The isomerization from the H-H to the H-T conformation is feasible, whereas next substitutions of the cod ligand by CO first, and PMe3 later confirm the H-T coordination as the thermodynamically preferred. It is envisaged the exchange of the metal, from iridium to rhodium, confirming here the innocence of the nature of the metal for such arrangements of the bridging ligands
A.P. thanks the Spanish MINECO for a project CTQ2014-59832-JIN
Format: application/pdf
Accés al document: http://hdl.handle.net/10256/13188
Llenguatge: eng
Editor: Beilstein-Institut
Col·lecció: info:eu-repo/semantics/altIdentifier/doi/10.3762/bjoc.12.13
info:eu-repo/semantics/altIdentifier/eissn/1860-5397
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/
Drets: Attribution 3.0 Spain
URI Drets: http://creativecommons.org/licenses/by/3.0/es/
Matèria: Funcional de densitat, Teoria del
Density functionals
Isomerització
Isomerization
Ruteni -- Compostos
Ruthenium compounds
Iridi
Iridium
Compostos heterocíclics
Heterocyclic compounds
Títol: Versatile deprotonated NHC: C,N-bridged dinuclear iridium and rhodium complexes
Tipus: info:eu-repo/semantics/article
Repositori: DUGiDocs

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