Ruthenium thiocarbonyl and phosphoniodithiocarboxylate complexes with an oxygen tripod ligand

Treatment of [Ru(CO)(2)Cl-2](x) with NaLOEt (L-OEt(-) = [Co(eta(5)-C5H5){P( O)(OEt)(2)}(3)](-)) afforded [LOEtRu(CO)(2)Cl] (1), which reacted with AgBF 4 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-tay crystallography. The Ru-C, Ra-P, Ru-Cl and average Ru-O distances in 3 are 1.993(7), 2.2811(13), 2.376(2) and 2.137 Angstrom, respectively. Interaction of [LOEtRu(PPh3)(2)Cl] with CS2 and PR3 in the pr esence of [NH4][PF6] afforded the ruthenium(II) phosphoniodithiocarboxylate species [LOEtRu(PPh3)(eta(2)-S2CPR3)][PF6] (R=Ph (4) or cyclohexyl (5)). O xidation of 4 with AgBF4 yielded the ruthenium(III) complex [LOEtRu(PPh3)(e ta(2)-S2CPPh3)][BF4][PF6] (6), which has been characterized by X-ray crysta llography. The Ru-P, average Ru-O and average Ru-S distances in 6 are 2.397 8(10), 2.078 and 2.2910 Angstrom, respectively. The ruthenium(II) thiocarbo nyl complex [LOEtRu(CS)Cl(PPh3)] (7) was prepared from NaLOEt and [Ru(CS)Cl -2(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 Angstrom, respectively. Treatmen t 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 stro nger pi acid ligand than CO. (C) 2000 Elsevier Science S.A. All rights rese rved.