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Issue 2, 2009
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Dinuclear gold(I) and gold(III) complexes of bridging functionalized bis(N-heterocyclic carbene) ligands: synthesis, structural, spectroscopic and electrochemical characterizations

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Abstract

We report the synthesis of Au(I) and Au(III) complexes, involving alcohol functionalized bis(N-heterocyclic carbene) ligands. Two short reaction pathways lead to the diimidazolium precursors, namely 1,1′-(2,6-pyridinediyl)bis[3-(2-hydroxyethyl)-1H-imidazol-3-ium]diiodide (2), 3,3′(methanediyl)bis[1-(2-hydroxy-2-methylpropyl)-1H-imidazol-3-ium]dibromide (4) and 3,3′-(1,3-propanediyl)bis[1-(2-hydroxy-2-methylpropyl)-1H-imidazol-3-ium]bis(4-methylbenzenesulfonate) (6), in which the two azolium rings are bridged by a rigid pyridine unit or an aliphatic chain (C1 or C3). The Au(I) complexes [AuI(Lpy)]22+[PF6]2 (11) and [AuI(LC1)]22+[PF6]2 (13) were obtained by direct metallation of the salts 2 and 4, respectively, in the presence of sodium acetate with Au(SMe2)Cl, followed by an anionic metathesis in the presence of KPF6. The trimethylene compound [AuI(LC3)]22+[PF6]2 (15) was prepared by transmetallation between the related precursor [AgI(LC3)]22+[PF6]2 (10) and Au(SMe2)Cl. The Au(III) complexes, [AuIII(Lpy)Br2]22+[PF6]2 (16), [AuIII(LC1)Br2]22+[PF6]2 (17) and [AuIII(LC3)Br2]22+[PF6]2 (18) were generated by oxidation of the corresponding Au(I) species with an excess of elemental bromine. Complexes 11, [AuI(LC1)]22+[Br]2 (12) and 15 have been characterized by single-crystal X-ray diffraction analyses. The electrochemical and luminescence properties of the Au(I) and Au(III) compounds have been studied.

Graphical abstract: Dinuclear gold(i) and gold(iii) complexes of bridging functionalized bis(N-heterocyclic carbene) ligands: synthesis, structural, spectroscopic and electrochemical characterizations

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The article was received on 11 Jun 2008, accepted on 08 Sep 2008 and first published on 06 Nov 2008


Article type: Paper
DOI: 10.1039/B809943J
Citation: Dalton Trans., 2009,0, 340-352
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    Dinuclear gold(I) and gold(III) complexes of bridging functionalized bis(N-heterocyclic carbene) ligands: synthesis, structural, spectroscopic and electrochemical characterizations

    F. Jean-Baptiste dit Dominique, H. Gornitzka, A. Sournia-Saquet and C. Hemmert, Dalton Trans., 2009, 0, 340
    DOI: 10.1039/B809943J

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