Spectroscopic and electrochemical observation of both 17- and 19-electron states of an inorganometallic transition metal complex: [FeIII(η5-C5Me5)(S2CNMe2)2]

Abstract

The blue 19e complex [Fe^III(C₅Me₅)(η²-S₂CNMe₂)₂]1, generated by addition of NaS₂CNMe₂ to the 17e complex [Fe^III(C₅Me₅)(η²-S₂CNMe₂)(MeCN)]PF₆ in MeCN at –45 °C or by monoelectronic reduction of the 18e cation 1⁺ using the 19e complex [Fe^I(C₅H₅)(C₆Me₆)] in THF at –80 °C gives the purple 17e form [Fe^III(C₅Me₅)(η²-S₂CNMe₂)-{η¹-SC(S)NMe₂}]2 in solution and in the solid state; both the 17e and 19e forms are characterized by their specific ESR and Mössbauer spectra and by cyclic voltammetry.