Bis- and tetrakis-(diphenylphosphino) tetrathiafulvalenes as precursors of redox-active organic—inorganic polymeric networks
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Lithiation of the (Z)-, (E)-dimethyltetrathiafulvalene mixture and subsequent reaction with ClPPh2 afford (Z)- and (E)-dimethylbis(diphenylphosphino)tetrathiafulvalene which are separated by fractional recrystallization. The identity of (Z)-P2 has been ascertained by its X-ray crystal structure determination. By similar methods, tetrakis(diphenylphosphino)tetrathiafulvalene (P4) is obtained from the tetrathiafulvalene tetralithium derivative. Cyclic voltammetry experiments reveal that the new compounds oxidize reversibly in two one-electron steps to the radical cation and dication. Reaction of 0-P2 with the dinuclear complex [Rh2(NCCH3)10](BF4)4 has been investigated and found to produce the square-planar Rh(I) compound [(0-P2)2Rh][BF4]. The identity of the product has been confirmed by X-ray crystallography, FAB-MS, elemental analysis, and NMR spectroscopy. Several reactions of solvated cations were also performed, all of which appear to lead to products with 0-P2 and P4 ligands.
author list (cited authors)
Fourmigué, M., Uzelmeier, C. E., Boubekeur, K., Bartley, S. L., & Dunbar, K. R.