Issue 5, 2001
From the journal:

Journal of the Chemical Society, Dalton Transactions

Square-planar rhodium(I) complexes with aromatic bent terdentate nitrogenligands as candidates for rod-like extended materials †

Jean-Marc Bénech,a   Claude Piguet,*a   Gérald Bernardinelli,b   Jean-Claude G. Bünzlic  and  Gérard Hopfgartnerd  

* Corresponding authors

a Department of Inorganic, Analytical and Applied Chemistry, University of Geneva, 30 quai E. Ansermet, 4, Geneva, Switzerland
E-mail: Claude.Piguet@chiam.unige.ch

b Laboratory of X-ray Crystallography, 24 quai E. Ansermet, 4, Geneva, Switzerland

c Institute of Inorganic and Analytical Chemistry, University of Lausanne, BCH 1402, Lausanne, Switzerland

d F. Hoffmann-La Roche Ltd, Pharmaceuticals Division, PRNS 68/142, Basle, Switzerland

Abstract

The crystal structure of 2,6-bis(1-methylbenzimidazol-2-yl)pyridine (L4) evidenced a quasi trans-trans conformation of the unsubstituted nitrogen atoms of the aromatic rings which is maintained in solution on the NMR timescale. Reactions of L4, or of its lipophilic analogue 2,6-bis(1-octylbenzimidazol-2-yl)pyridine (L5), with [Rh(NBD)Cl]2 (NBD = bicyclo[2.2.1]hepta-2,5-diene) produced poorly soluble dimetallic complexes [{Rh(NBD)Cl}2Li] (i = 4 or 5). The crystal structure of [{Rh(NBD)Cl}2L5] revealed that the terdentate aromatic unit adopts a distorted trans-trans conformation and acts as a bridging ligand connecting two [Rh(NBD)Cl] units through the nitrogen atoms of the benzimidazole side arms. Solution studies (ES-MS, NMR) indicate that (i) the dimetallic structure is maintained in solution, (ii) the complicated fluxional behaviour observed at room temperature is blocked at 210 K on the NMR timescale and (iii) the bent aromatic core cannot act as a meridional terdentate chelate toward RhI. The consequences of this co-ordination behaviour on the molecular anisometry of extended complexes is discussed.

Graphical abstract: Square-planar rhodium(I) complexes with aromatic bent terdentate nitrogen ligands as candidates for rod-like extended materials [ ]

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Article information

DOI
https://doi.org/10.1039/B009051O
Article type
Paper
Submitted
10 Nov 2000
Accepted
20 Dec 2000
First published
15 Feb 2001

J. Chem. Soc., Dalton Trans., 2001, 684-689

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Square-planar rhodium(I) complexes with aromatic bent terdentate nitrogen ligands as candidates for rod-like extended materials

J. Bénech, C. Piguet, G. Bernardinelli, J. G. Bünzli and G. Hopfgartner, J. Chem. Soc., Dalton Trans., 2001, 684 DOI: 10.1039/B009051O

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