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Abstract:
Some new developments in dithiolene molybdenum model chemistry, in particular focusing on structural aspects of molybdopterin, will be presented. These are, for instance, synthesis, characterisation and reactivity of pyrane dithiolene complexes of molybdenum and tungsten and derivatives thereof. Chemical, electrochemical and catalytic
properties were studied in comparison in order to further understand the role of the pyrane unit in molybdopterin. The pyrazine ring in combination with the dithiolene moiety has been addressed separately. Among intended outcomes of the various synthetic approaches, some unexpected and pleasantly surprising observations were made [1, 2]. These are for instance unusual binding motifs found crystallographically (e.g. dithiolene-sulfur hydrogen bonds, interactions involving the M=O moiety and packing motifs; Fig.), the discovery of a very mild synthetic route to pentathiepins and the unexpectedly facile oxidation of complexes by air. Generous financial support by the ERC is gratefully acknowledged (project: MocoModels).
