15663-30-6Relevant articles and documents
Surface-assisted synthesis and behavior of dimetallic mixed-metal complexes [M2Cl2(μ-Cl)4(CO)6M′(L) 2] (M = Ru, Os; M′ = Fe, Co; L = CH3CH 2OH, H2O)
Jakonen, Minna,Hirva, Pipsa,Nivajaervi, Taina,Kallinen, Mirja,Haukka, Matti
, p. 3497 - 3508 (2008/03/13)
The reductive carbonylation of ruthenium and osmium halides in the presence of cobalt and iron surfaces was studied. In these surface-assisted reactions the metal surface plays an active role in releasing metal ions, which can be used for the in situ synthesis of mixed-metal compounds. A linear, dimetallic, chlorido-bridged, trinuclear complex [Ru2Cl2(μ-Cl) 4(CO)6Co(CH3CH2OH)2] was obtained by the interaction between reducing RuCl3 and the cobalt surface. In the reaction the RuCl3 is reduced with carbon monoxide in the presence of a solid cobalt surface in ethanol solution. During the reduction of the RuCl3 the cobalt surface was simultaneously corroded, releasing cobalt cations. In addition to [Ru2Cl 2(μ-Cl)4(CO)6Co(CH3CH 2OH)2], the reaction also produced other trinuclear complexes and mononuclear products, such as a bent and linear dimetallic, chlorido-bridged complex with the aqua ligand [Ru2Cl 2(u-Cl)4(CO)6Co(H2O)2] and ionic [RuCl3(CO)3]2[Co(H2O) 6], The carbon monoxide reduction of Rul3 produced the ionic complex [RuI3(CO)3]2[M′(H 2O)6] (M′ = Fe, Co) in the presence of iron, stainless steel or cobalt. Iodido-bridged trinuclear mixed-metal complexes were not observed. The surface-assisted process proved to be useful with other metal combinations as well. When RuCl3 was replaced with OsCl3, a variety of trinuclear mixed-metal complexes, such as [Os2Cl 2(u-Cl)4(CO)6Co(CH3CH 2OH)2] and ionic [OsCl3(CO)3] 2[M(H2O)6] (M = Fe, Co), were obtained, depending on the metal surface used. Due the lability of the chlorido-bridged trinuclear complexes, the possible decomposition steps of [M2Cl 2(μ-Cl)4(CO)6M′(CH3CH 2OH)2] (M = Ru, Os; M′ = CO, Fe) were studied computationally, using DFT methods. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.
