Electronic structure and metal-metal bonding in nominal d3d3 MIIMIVCL93- (MII = V, Nb, Ta; MIV = Mn, Tc, Re) face-shared binuclear complexes

Robert Stranger*, Simon Petrie

*Corresponding author for this work

    Research output: Contribution to journalArticlepeer-review

    7 Citations (Scopus)

    Abstract

    Density functional theory (DFT) calculations have been employed to study structural and electronic configuration trends in the series of mixed-group, face-shared, bimetallic complexes M′M″Cl93- (M′ = V, Nb, Ta; M″ = Mn, Tc, Re), in which each metal possesses a nominal d3 valence electronic configuration. While the tendency of complexes to exhibit either multiple metal-metal bonded structures (with short intermetallic separations) or weakly-coupled systems (characterized by large intermetallic distances) is broadly consistent with that seen in our earlier studies on same-group dimers (e.g. Cr2Cl93-), there are also several novel structural and electronic effects which are directly attributable to electron transfer from MII to MIV. The general tendency towards intermetallic electron transfer is well modelled by a simple expression involving the spin polarization energy of each metal, and the ligand-field splitting of t2g and eg orbitals, in the corresponding d3-valence hexachloro octahedral complex. The effects of this electron transfer include, in some instances, a preference towards ferromagnetic coupling between metal atoms; diminished barriers to complex dissociation; and formation of edge-shared dimers with one five-coordinate metal atom. The heavier congeners, i.e. those lacking V and Mn, are predicted to have strong multiple metal-metal bonds with significant barriers to dissociation.

    Original languageEnglish
    Pages (from-to)3630-3639
    Number of pages10
    JournalJournal of the Chemical Society. Dalton Transactions
    Issue number18
    DOIs
    Publication statusPublished - 2002

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