Electrocrystallization and characterization of phosphonium-based radical anion salts [MePh3P] [Pd(dmit)2]3 and [Ph4P] [Pd(dmit)2]3 (dmit = 1,3-dithiole-2-thione-4,5-dithiolate). Comparison with related Pd and Ni isologues

Anthony E. Pullen, Christophe Faulmann, Hsiang Lin Liu, D. B. Tanner, Khalil A. Abboud, John R. Reynolds

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The two new radical anion salts [MePh3P] [Pd(dmit)2]3 (1) (dmit = C3S52 = 1,3-dithiole-2-thione-4,5-dithiolate) and [Ph4P]-[Pd(dmit)2]3 (2) have been synthesized and characterized by X-ray diffraction, elemental analysis and temperature-dependent conductivity measurements. Complexes 1 and 2 were prepared via electrooxidation of [Pd(dmit)2]2- in acetonitrile-acetone solvent mixtures at a Pt wire anode in the presence of methyltriphenylphosphonium bromide and tetraphenylphosphonium bromide electrolytes, respectively. For [MePh3P] [Pd(dmit)2]3 (1), black shiny needle and platelet crystals suitable for X-ray analysis were obtained. The crystal packing structure consists of layers of Pd(dmit)2 units separated by layers of MePh3P+ counterions. The Pd(dmit)2 layers are composed of dimers of Pd(dmit)2 units as a result of strong Pd⋯Pd interactions. Extensive S⋯S nonbonding interdimer intera ctions are observed, with each dimer interacting with six other adjacent dimers. For [Ph4P] [Pd(dmit)2]3 (2), black shiny flat needles were harvested and th e stoichiometry confirmed by elemental analysis. Single-crystal temperature-dependent conductivity measurements show that 1 behaves as a semiconductor with a room-temperature conductivity of 13 S cm-1 and a thermal activation energy of 100 meV. Compound 2 also displays semiconducting behavior with a room-temperature conductivity of 0.8-1 S cm-1 and a thermal activation energy of 55 meV.

Original languageEnglish
Pages (from-to)90-95
Number of pages6
JournalInorganica Chimica Acta
Issue number1
Publication statusPublished - 1998 Nov 10



  • Crystal structures
  • Dithiolate complexes
  • Electrocrystallization
  • Palladium complexes
  • Phosphonium complexes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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