The Dithiocarbonate Route to 1,2-Dithiolene Complexes of Molybdenum and Tungsten

Xiaoguang Yang, Gavin K.W. Freeman, Thomas B. Rauchfuss, Scott R. Wilson

Research output: Contribution to journalArticlepeer-review


Tetrathiapentalenedione, C2S4(CO)2, reacts with MS42- (M = Mo, W) to give M(S2C2S2CO3)2-, isolated as PPh4+ salts. COS is the major coproduct of this transformation. The new tris(dithiolene) complexes were characterized by spectroscopic methods as well as a crystallographic study of (PPh4)2[W(S2C2S2CO) 3]. C2S4(CO)(CS) and WS42- react to give W(S2C2S2CS)32- together with [W2S4(S2C2S2CS) 2]2-. The same compounds can be obtained by the action of WS42- on the cyclic bis(disulfide) (S2C2S2CS)2. Electrochemical studies show that [M(S2C2S2CE)3]2- (M = Mo, W; E = S, O) undergo two one-electron oxidations at mild potentials. [Mo(S2C2S2CO)3]0 was prepared by the oxidation of the corresponding dianion with nitrosonium and ferrocenium salts. The neutral dithiolenes are soluble in nonpolar organic solvents and were characterized by IR and mass spectrometry. A methanol suspension of [Mo(S2C2S2CO)3]0 reacts with methoxide followed by methyl or butyl iodide to give the new dithiolenes [Mo(S2C2S2R2)3] 0. These species are less oxidizing than [Mo(S2C2S2CO)3]0.

Original languageEnglish (US)
Pages (from-to)3034-3038
Number of pages5
JournalInorganic Chemistry
Issue number15
StatePublished - Jul 1 1991

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry


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