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.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry