Addition of sulfur dioxide to ruthenium thiolate complexes, structure of a remarkably stable thiolate-SO2-adduct

Ruthenium thiolates [cpRu(PPh3)2(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) A, β = 90.141(5)deg, Z = 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. (orig.)