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Issue 9, 2013
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Vanadium–iron complexes featuring metal–metal multiple bonds

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Abstract

A series of V/Fe heterobimetallic complexes supported by phosphinoamide ligands, [Ph2PNiPr], is described. The V(III) metalloligand precursor [V(iPrNPPh2)3] can be treated with Fe(II) halide salts under reducing conditions to afford [V(iPrNPPh2)3FeX] (X = Br (2), I (3)). These complexes feature multiple bonds between Fe and V, leading to an intermetallic distance of ∼2.07 Å. Exploration of the one-electron reduction of complex 3 allows isolation of [V(iPrNPPh2)3Fe(PMe3)] (5), which also features metal–metal multiple bonding and a nearly identical Fe–V distance. Mössbauer spectroscopy of complexes 2 and 5 suggest that the most reasonable oxidation state assignments for these complexes are VIIIFeI and VIIIFe0, respectively, and that reduction occurs solely at the Fe center in these bimetallic complexes. A theoretical investigation confirms this description of the electronic structure, providing a description of the metal–metal bonding manifolds as (σ)2(π)4(Fenb)3 and (σ)2(π)4(Fenb)4 for complexes 3 and 5, consistent with a metal–metal bond order of three. One electron-oxidation of complex 3 results in halide abstraction from PF6, forming FV(iPrNPPh2)3FeI (6). Complex 6 has a much weaker V–Fe interaction as a result of axial fluoride ligation at the V center.

Graphical abstract: Vanadium–iron complexes featuring metal–metal multiple bonds

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Publication details

The article was received on 13 May 2013, accepted on 25 Jun 2013 and first published on 26 Jun 2013


Article type: Edge Article
DOI: 10.1039/C3SC51337H
Citation: Chem. Sci., 2013,4, 3557-3565
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    Vanadium–iron complexes featuring metal–metal multiple bonds

    S. Kuppuswamy, T. M. Powers, J. P. Krogman, M. W. Bezpalko, B. M. Foxman and C. M. Thomas, Chem. Sci., 2013, 4, 3557
    DOI: 10.1039/C3SC51337H

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