Redox Multifunctionality in a Series of PtII Dithiolene Complexes of a Tetrathiafulvalene-Based Diphosphine Ligand

The redox-active and chelating diphosphine, 3,4-dimethyl-3',4'-bis(diphenylphosphino)-tetrathiafulvalene, denoted as P2, is engaged in a series of platinum complexes, [(P2)Pt(dithiolene)], with different dithiolate ligands, such as 1,2-benzenedithiolate (bdt), 1,3-dithiole-2-thione-4,5-dithiolate (dmit), and 5,6-dihydro-1,4-dithiin-2,3-dithiolate (dddt). The complexes are structurally characterized by X-ray diffraction, together with a model compound derived from bis(diphenylphosphino)ethane, namely, [(dppe)Pt(dddt)]. Four successive reversible electron-transfer processes are found for the [(P2)Pt(dddt)] complex, associated with the two covalently linked but electronically uncoupled electrophores, that is, the TTF core and the platinum dithiolene moiety. The assignments of the different redox processes to either one or the other electrophore is made thanks to the electrochemical properties of the model compound [(dppe)Pt(dddt)] lacking the TTF redox core, and with the help of theoretical calculations (DFT) to understand the nature and energy of the frontier orbitals of the [(P2)Pt(dithiolene)] complexes in their different oxidation states. The first oxidation of the highly electron-rich [(P2)Pt(dddt)] complex can be unambiguously assigned to the redox process affecting the Pt(dddt) moiety rather than the TTF core, a rare example in the coordination chemistry of tetrathiafulvalenes acting as ligands.