Trinuclear transition metal complexes of formula [M3(μ3-O)(μ-LL)6X3]z , where LL = carboxylate and X = terminal ligand, have been studied for several decades with respect to their electronic structure, magnetic properties and relevance to metal-oxo cores of metalloproteins. While redox properties have been reported in a few cases, by and large these carboxylate-bridged species are too labile to withstand redox modification. In contrast, analogous complexes of LL = pyrazolate (or substituted pyrazolate) are quite robust, allowing access to redox-modified states. We have prepared [MIII3(μ3-O)(μ-pz*)6X3]z complexes, where pz* = substituted pyrazolato anion and M = Cr, Fe, Co. Electrochemical and bulk redox reactions have yielded the corresponding mixed-valence CrIII2CrIV, FeIII2FeIVand FeIII2FeII, among them high-spin (HS), low-spin (LS) and spin-crossover (SCO) species.

Trinuclear, basic metal pyrazolates: Redox activity and electronic structure

2019 Spring National Meeting

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