Cyclic voltammetry studies show that [(C5Me5)Rh(C4Me4S)]2+ undergoes two reversible one-electron reductions at low potentials. The reduced product was synthesized by cobaltocene reduction and was characterized as [(η5-C5Me5)Rh(η4-C 4Me4S)]. 1H and 13C NMR spectroscopic results are consistent with a symmetrical, reduced thiophene ligand. An X-ray crystallographic study confirms that the reduced complex contains a nonplanar η4-thiophene ligand with an uncoordinated sulfur atom. The reduced complex reacts with Fe3(CO)12 to give (C5Me5)RhC4Me4Fe(CO)3 which is analogous to a major product in the Fe3(CO)12 desulfurization of thiophenes. Electron-transfer activation is proposed to be relevant to the desulfurization of thiophenes by metal surfaces.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry