Mixed-Valent Polynuclear Cobalt Complexes Incorporating Tetradentate Phenoxyamine Ligands

Mixed-Valent Polynuclear Cobalt Complexes Incorporating Tetradentate Phenoxyamine Ligands The new potentially tetradentate ligand precursor 2-((bis(2-hydroxyethyl)amino)methyl)-4,6-bis- tert -butylphenol (H 3 L) has been synthesized and characterized. The reaction of H 3 L with cobalt( ii ) acetate has afforded the novel mixed-valent tetra- and pentanuclear cobalt complexes (Co II 2 Co III 2 (OAc) 2 (L) 2 (HL)) ( 1 ) and (Co II Co III 4 (OAc) 2 (L) 4 ) ( 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 4 A′ 2 ground term, allowing a spin-only treatment assuming local spin quantum numbers of S i = 3/2. Fitting the data to the Heisenberg exchange Hamiltonian (Ĥ ex = –2 J S · 1 S 2 ) results in J = –6.9(1) cm –1 and g = 2.30(5). http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Australian Journal of Chemistry CSIRO Publishing

Mixed-Valent Polynuclear Cobalt Complexes Incorporating Tetradentate Phenoxyamine Ligands

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