Formation and Structural Characterization of [RuCl2(CO) 2(SPh2)2], [RuCl2(CO) 3(OH2)], and [Ru(OH2)6][RuCl 3(CO)3]2·2H2O

While the room temperature reaction of [RuCl2(CO) 3]2 and Ph2S in tetrahydrofuran in air affords [RuCl2(CO)2(SPh2)2] (1) in moderate yield, that in dichloromethane results in the formation of a mixture of [RuCl2(CO)3(H2O)] (2) and [Ru(H 2O)6][RuCl3(CO)3] 2·2H2O (3). Very small amounts of 1 are produced only upon prolonged reflux of the reagents. All compounds were characterized by X-ray crystallography. 1 crystallizes as discrete octahedral cis(CO), cis(Cl), trans(Ph2S) complexes, which are joined into stacks by weak H⋯Cl hydrogen bonds. 2 is also composed of discrete octahedral complexes. Four hydrogen bonds involving aqua and chlorido ligands link two complexes into a dimer. The structure of 3 consists of octahedral hexaaquaruthenium cations and two tricarbonyl-trichloridoruthenate anions. The water of crystallization is involved in hydrogen bonding between the cations and anions resulting in the formation of a continuous three-dimensional network.