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Transition metal bound thiolates play essential roles in bioinorganic electron transfer and catalytic processes. Understanding the bonding between the sulfur and the metal atoms are important for gaining insight into the structural and functional
relationship. The most studied are the bis(dithiolato)transition metal complexes. The hotly debated question is whether dithiolenes can act as innocent or non-innocent ligands. In this work an unambiguous assignment of the spectroscopic oxidation states
of the ligand in a series of bis(3,5-di-tert-butylbenzodithiolate)-transition metal complexes has been done by a combination of crystallographic, spectroscopic (IR, resonance Raman, UV-vis, Mössbauer, EPR) and advanced computational
(Relativistic DFT and ab initio) methods. In particular, UV-Vis, Infrared, and resonance Raman spectroscopy are found to be of immense importance in the unequivocal detection of S,S-coordinated 1,2-dithiobenzosemiquinonate(1-) radicals in
coordination compounds.
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