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

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

doi:10.1021/ic00015a018

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

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

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

Tetrathiapentalenedione, C₂S₄(CO)₂, reacts with MS₄^2- (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 WS₄^2- react to give W(S₂C₂S₂CS)₃^2- together with [W₂S₄(S₂C₂S₂CS) ₂]^2-. The same compounds can be obtained by the action of WS₄^2- 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 language	English (US)
Pages (from-to)	3034-3038
Number of pages	5
Journal	Inorganic Chemistry
Volume	30
Issue number	15
DOIs	https://doi.org/10.1021/ic00015a018
State	Published - Jul 1 1991

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Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/ic00015a018

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

abstract = "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.",

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AU - Yang, Xiaoguang

AU - Freeman, Gavin K.W.

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AU - Wilson, Scott R.

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N2 - 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.

AB - 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.

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

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