Ruthenium thiocarbonyl and phosphoniodithiocarboxylate complexes with an oxygen tripod ligand

Abstract

Treatment of [Ru(CO) 2Cl 2] x with NaL OEt (L OEt −=[Co(η 5-C 5H 5){P(O)(OEt) 2} 3] −) afforded [L OEtRu(CO) 2Cl] ( 1), which reacted with AgBF 4 in acetone–H 2O to give [L OEtRu(CO) 2(H 2O)][BF 4] ( 2). Reaction of [L OEtRu(CHCHPh)(CO)(PPh 3)] with HCl gave [L OEtRuCl(CO)(PPh 3)] ( 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 Å, respectively. Interaction of [L OEtRu(PPh 3) 2Cl] with CS 2 and PR 3 in the presence of [NH 4][PF 6] afforded the ruthenium(II) phosphoniodithiocarboxylate species [L OEtRu(PPh 3)(η 2-S 2CPR 3)][PF 6] (R=Ph ( 4) or cyclohexyl ( 5)). Oxidation of 4 with AgBF 4 yielded the ruthenium(III) complex [L OEtRu(PPh 3)(η 2-S 2CPPh 3)][BF 4][PF 6] ( 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 Å, respectively. The ruthenium(II) thiocarbonyl complex [L OEtRu(CS)Cl(PPh 3)] ( 7) was prepared from NaL OEt and [Ru(CS)Cl 2(PPh 3) 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 Å, respectively. Treatment of 7 with AgBF 4 in acetone–H 2O afforded [L OEtRu(CS)(PPh 3)(H 2O)][BF 4] ( 8). On the basis of the Ru(III/II) formal potential, CS was found to be a stronger π acid ligand than CO.