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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 Journal of Organic Chemistry, 2016, vol. 12, p. 117-124

Beilstein-Institut

Author: Poater Teixidor, Albert
Date: 2016 January 22
Abstract: 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
Citation: 025566
Document access: http://hdl.handle.net/10256/13188
Language: eng
Publisher: Beilstein-Institut
Collection: MINECO/PE 2015-2018/CTQ2014-59832-JIN
Reproducció digital del document publicat a: http://dx.doi.org/10.3762/bjoc.12.13
Articles publicats (D-Q)
Is part of: Beilstein Journal of Organic Chemistry, 2016, vol. 12, p. 117-124
Rights: Attribution 3.0 Spain
Rights URI: http://creativecommons.org/licenses/by/3.0/es/
Subject: Funcional de densitat, Teoria del
Density functionals
Isomerització
Isomerization
Ruteni -- Compostos
Ruthenium compounds
Iridi
Iridium
Compostos heterocíclics
Heterocyclic compounds
Title: Versatile deprotonated NHC: C,N-bridged dinuclear iridium and rhodium complexes
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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