Jump to main content
Jump to site search

Issue 9, 2013
Previous Article Next Article

Vanadium–iron complexes featuring metal–metal multiple bonds

Author affiliations


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

Back to tab navigation

Supplementary files

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
  •   Request permissions

    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

Search articles by author