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DOI: 10.1039/A900578A (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1999, 2237-2242

Chelate complexes of cobalt(III) with bis(dithiolate) ligands: backbone influence on the electronic properties and the reactivity of the metal center

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Wolfram W. Seidel and F. Ekkehardt Hahn

Abstract

The tetradentate bis(dithiolate) ligands 1,4-bis[(2,3-disulfanylbenzamido)methyl]benzene H4L1 and 1,7-bis(2,3-disulfanylbenzamido)heptane H4L2 were prepared and converted into the dinuclear titanocene complexes [(TiCp2)2(L1)] 1 and [(TiCp2)2(L2)] 2, respectively. A ligand transfer reaction of 1 and 2 with [NR4]2[CoCl4] (R = Et or Me) led to the formation of the bis(dithiolato)cobaltate(III) complexes [NEt4][Co(L1)] 3 and [NR4][Co(L2] (R = Et 4a or Me 4b). The anion [Co(L2)]– adopts an approximately square-planar co-ordination geometry. Two anions are connected by intermolecular Co–S contacts at the apical position of the metal to form [Co(L2)]22–. In contrast, mononuclear 3 turned out to be unstable with respect to its co-ordination polymer. This phenomenological difference between 3 and 4a, 4b is reflected in the UV-VIS and cyclic voltammetry data of the complexes, which are compared to the data of the corresponding prototype complex tetraethylammonium [bis(3-N-benzylcarbamoylbenzene-1,2-dithiolato)cobaltate(III)] 5 with two unbridged dithiolato-ligands (L3)2–.

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