Metal-Metal Bonding in Trinuclear, Mixed-Valence [Ti3X12]4- (X = F, Cl, Br, I) Face-Shared Complexes

Jinasena W. Hewage, Germán Cavigliasso, Robert Stranger*

*Corresponding author for this work

    Research output: Contribution to journalArticlepeer-review

    2 Citations (Scopus)


    Metal-metal bonding in structurally characterized In4Ti3Br12, comprising linear, mixed-valence d1d2d1 face-shared [Ti3Br12]4- units with a Ti-Ti separation of 3.087 Å and strong antiferromagnetic coupling (Θ = -1216 K), has been investigated using density functional theory. The antiferromagnetic configuration, in which the single d electron on each terminal TiIII (d1) metal center is aligned antiparallel to the two electrons occupying the central TiII (d2) metal site, is shown to best agree with the reported structural and magnetic data and is consistent with an S = 0 ground state in which two of the four metal-based electrons are involved in a two-electron, three-center σ bond between the Ti atoms (formal Ti-Ti bond order of ∼0.5). However, the unpaired spin densities on the Ti sites indicate that while the metal-metal σ interaction is strong, the electrons are not fully paired off and consequently dominate the ground state antiferromagnetic coupling. The same overall partially delocalized bonding regime is predicted for the other three halide [Ti3X12]4- (X = F, Cl, I) systems with the metal-metal bonding becoming weaker as the halide group is descended. The possibility of bond-stretch isomerism was also examined where one isomer has a symmetric structure with identical Ti-Ti bonds while the other is unsymmetric with one short and one long Ti-Ti bond. Although calculations indicate that the latter form is more stable, the barrier to interconversion between equivalent unsymmetric forms, where the short Ti-Ti bond is on one side of the trinuclear unit or the other, is relatively small such that at room temperature only the averaged (symmetric) structure is likely to be observed.

    Original languageEnglish
    Pages (from-to)10632-10641
    Number of pages10
    JournalInorganic Chemistry
    Issue number22
    Publication statusPublished - 2 Nov 2015


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