Azido, Cyanato, and Thiocyanato Coordination Induced Distortions in Pentacoordinated [Co(II)A(bip)](2) (A = NCS-, N-3(-), or NCO-) Complexes

作者：Sarkar Mrinal; Clerac Rodolphe; Mathoniere Corine; Hearns Nigel G R; Bertolasi Valerio; Ray Debashis^*

来源：European Journal of Inorganic Chemistry, 2009, 2009(31): 4675-4685.

DOI：10.1002/ejic.200900577

• N,O ligands
• Bridging ligands
• Cobalt
• Structure elucidation
• Magnetic properties

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

• 出版日期2009-11