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 [Ru 2 Cl 2 (µ-Cl) 4 -(CO) 6 Co(CH 3 CH 2 OH) 2 ] was obtained by the interaction between reducing RuCl 3 and the cobalt surface. In the reaction the RuCl 3 is reduced with carbon monoxide in the presence of a solid cobalt surface in ethanol solution. During the reduction of the RuCl 3 the cobalt surface was simultaneously corroded, releasing cobalt cations. In addition to [Ru 2 Cl 2 (µ-Cl) 4 (CO) 6 Co(CH 3 CH 2 OH) 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 [Ru 2 Cl 2 (µ-Cl) 4 (CO) 6 Co(H 2 O) 2 ] and ionic

The use of iron-containing metal surfaces, Fe, Fe-Cr-alloy and stainless steel, for the synthesis of mixed metal Ru-Fe compounds has been studied. The studied process was reductive carbonylation of RuCl3 in the presence of a metal surface. Reactions were carried out in ethanol solutions under 10-50 bar carbon monoxide pressure at 125 degrees C using an autoclave. During the reaction the metal surface was oxidized, releasing iron into the solution and acting as a sacrificial source of iron. Under these conditions the corrosion of the metal surface was facile and produced a series of iron-containing species. In addition to the formation of most obvious iron(II) products, such as [Fe(H2O)6]2+ or [FeCl2(H2O)4] the use of the metal surface also provided a route to novel labile trinuclear [Ru2Cl2(mu-Cl)4(CO)6FeL2] (L = H2O, EtOH) complexes. The stability and reactivity of the [Ru2Cl2(mu-Cl)4(CO)6FeL2] complexes were further studied using computational DFT methods. Based on the computational results a reaction route has been suggested for the formation and decomposition of [Ru2Cl2(mu-Cl)4(CO)6FeL2].

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