Synthesis and characterization of heteroleptic redox active bismuth dithiolene and dithiolate complexes

Abstract

The “twelve principles of Green Chemistry” marked an important transition in the chemical industry’s view on waste - moving away from a waste management approach, and towards a waste reduction and prevention approach. The use of catalytic reagents in place of traditional stoichiometric ones is an important aspect of reducing the amount of waste generated during reactions. Transition metal complexes frequently used in redox catalysis, however, feature toxic metal centers which can be harmful to both human health and the environment. Bismuth has recently been the subject of interest as an alternative to toxic transition metal catalysts as redox non-innocent ligands can be used to make the otherwise redox inactive metal, redox active. The current study focuses on the use of dithiolenes and dithiolates as redox non-innocent ligands to impart redox activity on a heteroleptic bismuth complex. Two bismuth complexes, (Mes2Bi)2(tdt) and BiCl(tdt)-Py2, were synthesized and characterized by 1H and 13C{1H} NMR spectroscopy and X-ray crystallography.