Ruthenium(III) complexes containing dimethylsulfoxide or dimethylsulfide ligands, and a new route to trans-dichlorotetrakis(dimethylsulfoxide)ruthenium(II)

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Abstract
The new Ru(III) complex tran-[(dmso)2H]+[RuCl4(dmso)2]− (1) (dmso = S-bonded dimethylsulfoxide) has been synthesized. New synthetic routes are reported for mer-RuX3(dms)3 complexes (dms = dimethylsulfide, X = Cl (2) and Br (3)) and for trans-RuCl2(dmso)4 (4). The complexes have been studied spectroscopically while 1, 2 and 4 have also been characterized crystallographically. Crystals of 1 are monoclinic, P2/n, a = 9.280(3), b = 16.518(4), c = 14.034(3) Å, β = 100.78(2)°, Z = 4, ρc = 1.75 g cm−3. Crystals of 2 are orthorhombic, Pca21a = 10.764(2), b = 11.375(1), c = 12.243(1) Å, Z = 4, ρc = 1.74 g cm−3.Crystals of 4 are tetragonal, I4/m, a = 9.1256(8), c = 11.184(2) Å, Z = 2, ρc = 1.73 g cm−3. The structures were determined by heavy atom methods and were refined by full-matrix least-squares procedures to R (Rw) values of 0.030 (0.036), 0.025 (0.032), and 0.051 (0.071) for 3051, 3354, and 1205 reflections with I ≥ 3σ(I), respectively. The ionic complex 1 contains the protonated dmso cation [(dmso)2H]+, with the proton asymmetrically bonded between the two O atoms (O(3)—H(1) = 1.30(6); 0(4)—H(1) = 1.12(6) Å), and the [RuCl4(dmso)2]− octahedral anion with trans-disposed S-bonded dmso ligands. The structure determined for 4 duplicates one reported recently in the literature (E. Alessio etal. Inorg. Chem. 27, 4099 (1988)), and reveals all S-bonded dmso ligands; the Ru—Cl distance, 2.432(1) Å, is significantly longer than that reported, 2.402(2) Å. The dms complexes 2 and 3 were isolated unexpectedly from reaction of Ru salts with acidic dmso solutions. Keywords: ruthenium complexes, dimethylsulfoxide, dimethylsulfide, hydrogen bonding.