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

Research output: Contribution to journalArticle

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Abstract

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
Volume282
Issue number1
DOIs
Publication statusPublished - 1998 Nov 10

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Anions
Negative ions
Salts
Dimers
anions
salts
conductivity
dimers
needles
Needles
bromides
Activation energy
activation energy
Temperature
Crystals
Electrooxidation
X ray analysis
room temperature
Platelets
Acetone

Keywords

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

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

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

In: Inorganica Chimica Acta, Vol. 282, No. 1, 10.11.1998, p. 90-95.

Research output: Contribution to journalArticle

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T1 - 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

AU - Pullen, Anthony E.

AU - Faulmann, Christophe

AU - Liu, Hsiang Lin

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