Tri- and binuclear ruthenium carbonyl complexes containing bridging ligands derived from ortho-substituted anilines. A comparative study of their syntheses using RuCl3 center dot nH(2)O or [Ru-3(CO)(12)] as starting materials

The trinuclear carbonyl clusters [Ru-3(mu-H)(mu,eta(2)-o-HNC(6)H(2)Me(2)NH(2))(CO)(9)] (o-H(2)NC(6)H(2)Me(2)NH(2) = 1,2-diamino-4,5-dimethylbenzene) and [Ru-3(mu,eta(2)-o-OC6H4NH2)(2)(CO)(8)] (o-HOC6H4NH2 = 2-aminophenol) have been prepared by two alternative synthetic routes which involve (a) thermal reaction of [Ru-3(CO)(12)] with the appropriate ligand or (b) reaction of RuCl3 . nH(2)O with CO in refluxing 2-methoxyethanol, followed by treatment of the resulting solution with the appropriate ligand in the presence of zinc. However, [Ru-3(mu-H)(mu,eta(2)-o-SC6H4NH2)(CO)(9)](o-HSC6H4NH2 = 2-aminothiophenol) and [Ru-3(mu-H)(mu,eta(2)-o-OC6H4NH2)(CO)(9)] can only be prepared by method (a), whereas [Ru-2(mu,eta(2)-o-SC6H4NH)(CO)(6)] can only be prepared by method (b). The compound [Ru-3(mu-H)(mu,eta(2)-o-SC6H4NH2)(CO)(9)] has been characterized by X-ray diffraction methods: C15H7NO9Ru3S, orthorhombic, space group Pbca, a = 11.191(5), b = 16.462(5), c = 21.978(2) Angstrom, V = 4049(2) Angstrom(3), Z = 8, T = 293 K, R(F) = 0.043.