The reaction of dimethyl(methylthio)sulfonium tetrafluoroborate [(CH3)2S–SCH3][BF4] with η/5-cyclopentadienyl(dicarbonyl)carbyne complexes of molybdenum and tungsten Cp(CO)2M ≡ C–R (M = Mo, W; R = CH3, C6H5, C6H4CH3) 1c, 2a–d results in an electrophilic attack of the SCH3 moiety at the metal carbon triple bond, providing orange to red, diamagnetic, cationic η2-thiocarbene complexes 3c, 4a–d in high yields. The new compounds were identified by X-ray structure analysis, NMR, IR and mass spectra.
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