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Azido, Cyanato, and Thiocyanato Coordination Induced Distortions in Pentacoordinated [CoII A(bip)]2 (A = NCS–,N3–, or NCO–) Complexes

By M. Sarkar, R. Clérac, C. Mathonière, N. G. R. Hearns, V.Bertolasi and D. Ray


A new family of distorted pentacoordinate [Co2] complexes\ud was prepared and structurally characterized. In [CoIIA-(bip)]2·S(1–3)[A=NCS–,N3–, NCO–; S = dmf, MeOH, dcm;\ud Hbip = 2,6-bis(phenylmethyliminomethyl)-4-methylphenol],\ud the nonbonded Co···Co separations are in the 3.243 to\ud 3.254 Å range, and the pseudohalide-coordinated CoII\ud ionsare asymmetrically doubly bridged by the phenolate oxygen\ud atoms of the ligand. The complementary basal–apical (b–a)\ud and apical–basal (a–b) coordination modes of the phenolate\ud bridges of bip–offer one O and two N donors for metal-ion\ud coordination. In the three dinuclear complexes, the h.s.CoII\ud ions are coupled antiferromagnetically to yield a singlet\ud ground state. The solid-state variable-temperature magnetic\ud susceptibility measurement data on the complexes were fit-\ud ted to an isotropic Heisenberg dimer model that allowed esti-\ud mation of the antiferromagnetic interactions for 1–3

Topics: N, O ligands, Bridging ligands, Cobalt, Structure elucidation, Magnetic properties
Year: 2009
DOI identifier: 10.1002/ejic.200900577
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