The subtle effects of iron-containing metal surfaces on the reductive carbonylation of RuCl3.
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].
Haukka
Matti
M
Department of Chemistry, University of Joensuu, Department of Chemistry, P.O. Box 111, FI-80101 Joensuu, Finland. matti.haukka@joensuu.fi
Jakonen
Minna
M
Nivajärvi
Taina
T
Kallinen
Mirja
M