Reactivity of [CpCr(CO)3]2 towards thione (Cdouble bond; length as m-dashS) moieties in some sulfur-containing substrates

The reaction of [CpCr(CO)3]2 (Cp = η5-C5H5) (1) with 1 mol equivalent of 2,5-dimercapto-1,3,4-thiadiazole (triple bond; length of mdashDMcTH2) at ambient temperature led to the isolation of a reddish-brown crystalline solid of CpCr(CO)3(η1-DMcTH) (5) and a green solid of CpCr(CO)3H (2) in yields of ca. 28% and 30%, respectively, along with some [CpCr(CO)2]2 (3) and [CpCr(CO)2]2S (4). The reaction of 1 with 1 mol equivalent of vinylene trithiocarbonate (SCS(CH)2S) (triple bond; length of mdashVTTC) at 90 °C led to the isolation of a red crystalline solid of CpCr(CO)2(η2-SCHSC2H2) (6) in ca. 15% yield while the reaction of 1 with isopropylxanthic disulfide ((CH3)2CHOCS2)2 resulted in the formation of CpCr(CO)2(η2-S2COCH(CH3)2) (8) in ca. 80% yield. The complexes 5, 6 and 8 have been determined by single crystal X-ray diffraction analysis.