| Abstract: | Treatment of RuCl2(PPh3)3] with 2 equiv. HimtMPh (HimtMPh?=?1-(4-methyl-phenyl)-imidazole-2-thione) in the presence of MeONa afforded cis-Ru(κ 2-S,N-imtMPh)2(PPh3)2] (1), while interaction of RuCl2(PPh3)3] and 2 equiv. HimtMPh in tetrahydrofuran (THF) without base gave RuCl2(κ 1-S-HimtMPh)2(PPh3)2] (2). Treatment of RuHCl(CO)(PPh3)3] with 1 equiv. HimtMPh in THF gave RuHCl(κ 1-S-HimtMPh)(CO)(PPh3)2] (3), whereas reaction of RuHCl(CO)(PPh3)3] with 1 equiv. of the deprotonated imtMPh]? or imtNPh]? (imtNPh?=?1-(4-nitro-phenyl)-2-mercaptoimidazolyl) gave RuH(κ 2-S,N-imtRPh)(CO)(PPh3)2] (R?=?M 4a, R?=?N 4b). The ruthenium hydride complexes 4a and 4b easily convert to their corresponding ruthenium chloride complexes RuCl(κ 2-S,N-imtMPh)(CO)(PPh3)2] (5a) and RuCl(κ 2-S,N-imtNPh)(CO)(PPh3)2] (5b), respectively, in refluxing CHCl3 by chloride substitution of the RuH. Photolysis of 5a in CHCl3 at room temperature afforded an oxidized product RuCl2(κ 2-S,N-imtMPh)(PPh3)2] (6). Reaction of 6 with excess imtMPh]? afforded 1. The molecular structures of 1·EtOH, 3·C6H14, 4b·0.25CH3COCH3, and 6·2CH2Cl2 have been determined by single-crystal X-ray crystallography. |
