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Boskovic, Colette
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article
Mixed-valent polynuclear cobalt complexes incorporating tetradentate phenoxyamine ligands
Abstract
<p>The new potentially tetradentate ligand precursor 2-[(bis(2-hydroxyethyl) amino)methyl]-4,6-bis-tert-butylphenol (H<sub>3</sub>L) has been synthesized and characterized. The reaction of H<sub>3</sub>L with cobalt(ii) acetate has afforded the novel mixed-valent tetra- and pentanuclear cobalt complexes [Co<sup>II</sup><sub>2</sub>Co<sup>III</sup><sub>2</sub>(OAc) <sub>2</sub>(L)<sub>2</sub>(HL)] (1) and [Co<sup>II</sup>Co<sup>III</sup><sub>4</sub>(OAc)<sub>2</sub>(L)<sub>4</sub>] (2). Single-crystal X-ray diffraction studies of these complexes indicate different coordination geometries for the divalent cobalt centres in each complex, with distorted trigonal bipyramidal and distorted tetrahedral coordination evident in 1 and 2, respectively. The variable temperature magnetic susceptibility data for complex 1 reveal behaviour dominated by antiferromagnetic coupling between the two cobalt(ii) centres. Their approximate trigonal bipyramidal coordination geometries give rise to a <sup>4</sup>A′<sub>2</sub> ground term, allowing a spin-only treatment assuming local spin quantum numbers of S<sub>i</sub> = 3/2. Fitting the data to the Heisenberg exchange Hamiltonian (<sub>ex</sub> = 2JS<sub>1</sub>S<sub>2</sub>) results in J = 6.9(1) cm<sup>-1</sup> and g = 2.30(5).</p>