BIS-(DIPHENYLPHOSPHINO)TETRATHIAFULVALENES AND TETRAKIS-(DIPHENYLPHOSPHINO)TETRATHIAFULVALENES AS PRECURSORS OF REDOX-ACTIVE ORGANIC-INORGANIC POLYMERIC NETWORKS

Lithiation of the (Z)-, (E)-dimethyltetrathiafulvalene mixture and sub sequent reaction with ClPPh2 afford (Z)- and -dimethyl-bis(diphenylpho sphino)tetrathiafulvalene which are separated by fractional recrystall ization. The identity of(Z)-P-2 has been ascertained by its X-ray crys tal structure determination. By similar methods, tetrakis(diphenylphos phino)tetrathiafulvalene (P-4) is obtained from the tetrathiafulvalene tetralithium derivative. Cyclic voltammetry experiments reveal that t he new compounds oxidize reversibly in two one-electron steps to the r adical cation and dication. Reaction of o-P-2 with the dinuclear compl ex [Rh-2(NCCH3)(10)](BF4)(4) has been investigated and found to produc e the square-planar Rh(I) compound [(o-P-2)(2)Rh][BF4]. The identity o f the product has been confirmed by X-ray crystallography, FAB-MS, ele mental analysis, and NMR spectroscopy. Several reactions of solvated c ations were also performed, all of which appear to lead to products wi th o-P-2 and P-4 ligands.