Ruthenium thiolates [cpRu(PR′3)2(SR)] (PR′3 = PPh3,1/2 dppe, 1/2 dppm, R = Me, CH2Ph) are obtained from the corresponding chlorides and NaSR. PPh3 is readily exchanged for CO to give the chiral complexes [cpRu(PPh3)(CO)(SR)]. Alkylation with methyl tosylate yields the cations [cpRu(dppe)(SMeR)]+ and [cpRu(PPh3)(CO)(SMeR)]+, which were isolated as their PF6- salts. The neutral carbonyls add dimethyl acetylenedicarboxylate giving five-membered metallocycles.

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Ruthenium thiolates [cpRu(PPh3),(SMe)] and [cp*Ru(PPh2Me)2(SR)] (R = Me, Ph) react with sulfur dioxide in two different ways, substitution of phosphine for SO2, and addition of SO2 to the thiolate ligand. The structure of [cpRu(CO)(PPh3)(SMe · SO2)] was determined by X-ray crystallography: Crystals are monoclinic, space group P21/n, a = 10.26(9), b = 16.00(6), c = 14.73(6) Å, β = 90.141(5)°, Ζ = 4. The most remarkable feature is a very long (247,8 pm) S—S single bond. [cp*Ru(PPh2Me)(SO2)(SPh)] and the corresponding sulfur monoxide complex [cp*Ru(PPh2Me)(SO)(SPh)] undergo [3+2] cycloaddition with dimethylacetylene-dicarboxylate.

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