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Abstract
A series of complexes CpM(CO) n S 2CX (M = Mo, W; n = 2, 3; X = OR, SR; R = Me, Et) has been prepared by the reaction of xanthates and thioxanthates with CpM(CO) 3Cl. The dicarbonyl compounds are the exclusive products after sufficiently long reaction times and are produced at least partially through the tricarbonyl species as intermediates. The conversion of CpM(CO) 2S 2CX to CpM(CO) 2S 3CX is not a simple first-order process but is catalyzed by Cl − and/or S 2CX −. The tricarbonyl species can be alkylated at the uncoordinated sulfur atom to give ionic di- or tri-thiocarbonate complexes.
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