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Treatment of [Ru(CO)2Cl2]x with NaLOEt (LOEt−=[Co(η5-C5H5){P(O)(OEt)2}3]−) afforded [LOEtRu(CO)2Cl] (1), which reacted with AgBF4 in acetone–H2O to give [LOEtRu(CO)2(H2O)][BF4] (2). Reaction of [LOEtRu(CHCHPh)(CO)(PPh3)] with HCl gave [LOEtRuCl(CO)(PPh3)] (3), which has been characterized by X-ray crystallography. The RuC, RuP, RuCl and average RuO distances in 3 are 1.993(7), 2.2811(13), 2.376(2) and 2.137 A, respectively. Interaction of [LOEtRu(PPh3)2Cl] with CS2 and PR3 in the presence of [NH4][PF6] afforded the ruthenium(II) phosphoniodithiocarboxylate species [LOEtRu(PPh3)(η2-S2CPR3)][PF6] (R=Ph (4) or cyclohexyl (5)). Oxidation of 4 with AgBF4 yielded the ruthenium(III) complex [LOEtRu(PPh3)(η2-S2CPPh3)][BF4][PF6] (6), which has been characterized by X-ray crystallography. The RuP, average RuO and average RuS distances in 6 are 2.3978(10), 2.078 and 2.2910 A, respectively. The ruthenium(II) thiocarbonyl complex [LOEtRu(CS)Cl(PPh3)] (7) was prepared from NaLOEt and [Ru(CS)Cl2(PPh3)2]2. The RuCl, RuP, RuC and average RuO distances in 7 are 2.3681(10), 2.3043(9), 1.823(4), and 2.140 A, respectively. Treatment of 7 with AgBF4 in acetone–H2O afforded [LOEtRu(CS)(PPh3)(H2O)][BF4] (8). On the basis of the Ru(III/II) formal potential, CS was found to be a stronger π acid ligand than CO.