Octahedral hexanuclear iron clusters of the type [(HL)2Fe6(solv)x]n+, (x = 0, 2, 4, 6; n = –2, –1, 0, 1, 2, 3, 4) based on a weak field hexaamide ligand platform (HLH6 = (NH2-o-PhNHCH2)3CCH3) have been shown to be highly redox-active and capable of performing multi-site reduction of small molecules. The magnetic properties of these clusters are also redox-tunable, with giant spin ground states (S ≤ 19/2) readily accessible. These electronic and magnetic properties are highly dependent on the population of the frontier molecular orbitals with metal d electrons, and as such the dependence on metal type is of significant interest. Thus, the corresponding hexanuclear cobalt clusters, [(HL)2Co6(solv)x]n+, have also recently been synthesized, with an apparent similarity in redox profile (n = –1, 0, 1, 2, 3, 4). The electronic structure, magnetic properties, and reactivity of a family of these cobalt hexanuclear clusters will be discussed.

Synthesis and structure of octahedral cobalt clusters

255th National Meeting (2018)

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