Abstract

Dinuclear transition metal complexes with direct metal-metal interactions have the potential to generate unique reactivities and properties. Using asymmetric triazine ligands HN3tBuR (R = Et, iPr, nBu) featuring different alkyl substituents at 1,3-N centers, we report here the first rational synthesis of 'tetragonal lantern' type Fe(II) triazenides [Fe2(N3tBuR)4] [R = Et (1), iPr (2), nBu (3)] having an exceptionally short Fe-Fe distance (2.167-2.174 Å). Unlike the previously reported lantern structures with related amidinate or guanidinate ligands, highly air-sensitive 1-3 show a lower spin ground state, as indicated by Mössbauer, 1H NMR and DFT studies.

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