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

Bénech, Jean-Marc; Piguet, Claude; Bernardinelli, Gérald Hugues; Bünzli, Jean-Claude G.; Hopfgartner, Gerard

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Title		Square-planar rhodium(I) complexes with aromatic bent terdentate nitrogen ligands as candidates for rod-like extended materials
Authors		Bénech, Jean-Marc Piguet, Claude Bernardinelli, Gérald Hugues Bünzli, Jean-Claude G. Hopfgartner, Gerard
Published in		Dalton Transactions. 2001, no. 5, p. 684-689
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.
Identifiers		DOI: 10.1039/b009051o
Full text		Article (Author postprint) (269 Kb) - Limited access to UNIGE Other version: http://www.rsc.org/ej/DT/2001/b009051o.pdf
Structures		Faculté des sciences / Section des sciences pharmaceutiques Faculté des sciences / Section de chimie et biochimie / Département de chimie minérale, analytique et appliquée
Citation (ISO format)		BÉNECH, Jean-Marc et al. Square-planar rhodium(I) complexes with aromatic bent terdentate nitrogen ligands as candidates for rod-like extended materials. In: Dalton Transactions, 2001, n° 5, p. 684-689. https://archive-ouverte.unige.ch/unige:2347