Synthesis of Trinuclear Heterobimetallic Cyanido‐Bridged Complexes from the Reaction of [MnI(CN)(CO)(tBuNC)4] with Transition‐Metal Chlorides

Abstract

AbstractThe reaction of [Mn(CN)(CO)(tBuNC)4] with MnCl2·4H2O, FeCl3·9H2O, NiCl2·6H2O, and CuCl2·2H2O, respectively, led to the formation of trinuclear heterobimetallic complexes that comprised two manganese moieties, with each coordinating the corresponding metal chloride entities through cyanide bridges. The mixed‐valence trinuclear MnI–CN–MnII–NC–MnI complex as well as the MnI–CN–NiII–NC–MnI derivative have been characterized by X‐ray structure analyses. In the case of the copper and iron compounds that exhibit easily reducable central metal ions, intramolecular electron transfer from manganese(I) to copper(II) or iron(III), respectively, is shown by the presence of metal‐to‐metal charge‐transfer (MMCT) bands as well as by EPR spectroscopy. Moreover, the iron complex shows a subsequent disproportionation, which was demonstrated by the isolation and crystallographic characterization of the reduced species with two manganese(I) complex units coordinating one FeIICl2 moiety.