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Issue 11, 2014
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A metallacyclic alkyl-amido carbene complex (MCAAC)

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Abstract

The activation of the C[triple bond, length as m-dash]N moiety in the redox-active metalloligand [CpRu{κ3Npz-1}][PF6] (2) (1: ambidentate hybrid ligand, N[triple bond, length as m-dash]C–C(pz)3, with pz = pyrazolyl) was observed in the reaction with [Ir(cod)Cl]2 (cod = 1,5-cyclooctadiene). By performing detailed NMR spectroscopic and X-ray crystallographic investigations the product was found to be a bimetallic RuII–IrIII complex of the composition [CpRu{μ-1′}Ir(cod)Cl2][PF6] (3) consisting of a chemically modified ligand 1′. Most notably, the heterobimetallic complex 3 features an unprecedented metallacyclic alkyl-amido carbene (MCAAC) core structure, which is coordinated to an IrIII centre. Density functional theory (DFT) calculations as well as cyclic voltammetry (CV) studies were performed in an effort to establish the formal oxidation states of the metal atoms in 3. Indeed, a quasi-reversible oxidation wave was detected at E01/2 = 0.36 V, which was attributed to the RuII/RuIII redox couple, while two irreversible reduction processes were observed at very negative potentials and have been assigned to the stepwise reduction of IrIII to IrI. First efforts to elucidate the reaction mechanism have also been performed.

Graphical abstract: A metallacyclic alkyl-amido carbene complex (MCAAC)

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Publication details

The article was received on 19 Sep 2013, accepted on 08 Oct 2013 and first published on 24 Oct 2013


Article type: Paper
DOI: 10.1039/C3DT52591K
Citation: Dalton Trans., 2014,43, 4313-4319
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    A metallacyclic alkyl-amido carbene complex (MCAAC)

    I. Trapp, S. González-Gallardo, S. Hohnstein, D. Garnier, P. Oña-Burgos and F. Breher, Dalton Trans., 2014, 43, 4313
    DOI: 10.1039/C3DT52591K

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