Base Hydrolysis of Coordinated Thiophene: A Route from Thiophenes to Furans and the Preparation of [(C5Me5)RhS]4

Anton E. Skaugset; Thomas Rauchfuss; Scott R. Wilson

doi:10.1021/om00161a012

Base Hydrolysis of Coordinated Thiophene: A Route from Thiophenes to Furans and the Preparation of [(C₅Me₅)RhS]₄

Anton E. Skaugset, Thomas Rauchfuss, Scott R. Wilson

Chemistry

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

Abstract

The tetramethylthiophene (TMT) complex [Cp*Rh(TMT)]²⁺ (Cp* = C₅Me₅) undergoes hydrolytic cleavage of the C-S bond upon treatment with aqueous KOH. The product has the formula Cp*Rh(MeCOC₃Me₃S). A single-crystal X-ray diffraction study, as well as spectroscopic methods, showed that the compound contains Cp*Rh bound to an η⁴-acetylpropenethiolate group. HOSO₂CF₃ reverses the hydrolysis. Thermolysis of the ring-opened complex gives tetramethylfuran together with the cubane cluster [Cp*RhS]₄. The hydrolysis reaction was shown to apply to [Ru-(TMT)₂](OTf)₂ and [Ru(2,5-Me₂H₂C₄S)(cymene)](OTf)₂, which also gave acetylpropenethiolate complexes.

Original language	English (US)
Pages (from-to)	2875-2876
Number of pages	2
Journal	Organometallics
Volume	9
Issue number	11
DOIs	https://doi.org/10.1021/om00161a012
State	Published - 1990

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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10.1021/om00161a012

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@article{c71998685dca4f30ac2dc69cd1c0d11e,

title = "Base Hydrolysis of Coordinated Thiophene: A Route from Thiophenes to Furans and the Preparation of [(C5Me5)RhS]4",

abstract = "The tetramethylthiophene (TMT) complex [Cp*Rh(TMT)]2+ (Cp* = C5Me5) undergoes hydrolytic cleavage of the C-S bond upon treatment with aqueous KOH. The product has the formula Cp*Rh(MeCOC3Me3S). A single-crystal X-ray diffraction study, as well as spectroscopic methods, showed that the compound contains Cp*Rh bound to an η4-acetylpropenethiolate group. HOSO2CF3 reverses the hydrolysis. Thermolysis of the ring-opened complex gives tetramethylfuran together with the cubane cluster [Cp*RhS]4. The hydrolysis reaction was shown to apply to [Ru-(TMT)2](OTf)2 and [Ru(2,5-Me2H2C4S)(cymene)](OTf)2, which also gave acetylpropenethiolate complexes.",

author = "Skaugset, {Anton E.} and Thomas Rauchfuss and Wilson, {Scott R.}",

year = "1990",

doi = "10.1021/om00161a012",

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journal = "Organometallics",

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publisher = "American Chemical Society",

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TY - JOUR

T1 - Base Hydrolysis of Coordinated Thiophene

T2 - A Route from Thiophenes to Furans and the Preparation of [(C5Me5)RhS]4

AU - Skaugset, Anton E.

AU - Rauchfuss, Thomas

AU - Wilson, Scott R.

PY - 1990

Y1 - 1990

N2 - The tetramethylthiophene (TMT) complex [Cp*Rh(TMT)]2+ (Cp* = C5Me5) undergoes hydrolytic cleavage of the C-S bond upon treatment with aqueous KOH. The product has the formula Cp*Rh(MeCOC3Me3S). A single-crystal X-ray diffraction study, as well as spectroscopic methods, showed that the compound contains Cp*Rh bound to an η4-acetylpropenethiolate group. HOSO2CF3 reverses the hydrolysis. Thermolysis of the ring-opened complex gives tetramethylfuran together with the cubane cluster [Cp*RhS]4. The hydrolysis reaction was shown to apply to [Ru-(TMT)2](OTf)2 and [Ru(2,5-Me2H2C4S)(cymene)](OTf)2, which also gave acetylpropenethiolate complexes.

AB - The tetramethylthiophene (TMT) complex [Cp*Rh(TMT)]2+ (Cp* = C5Me5) undergoes hydrolytic cleavage of the C-S bond upon treatment with aqueous KOH. The product has the formula Cp*Rh(MeCOC3Me3S). A single-crystal X-ray diffraction study, as well as spectroscopic methods, showed that the compound contains Cp*Rh bound to an η4-acetylpropenethiolate group. HOSO2CF3 reverses the hydrolysis. Thermolysis of the ring-opened complex gives tetramethylfuran together with the cubane cluster [Cp*RhS]4. The hydrolysis reaction was shown to apply to [Ru-(TMT)2](OTf)2 and [Ru(2,5-Me2H2C4S)(cymene)](OTf)2, which also gave acetylpropenethiolate complexes.

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