Coordination behavior of amine bases to the axial site of a (dibenzo[b,i][1,4,8,11]tetraazacyclotetradecinato)cobalt(II)

Abstract

The mutual interaction of various amine bases with the (dibenzo[b,i][1,4,8,11] tetraazacyclotetradecinato)cobalt(II) (Co(II)-1) was investigated by measuring electronic spectra in methyl benzoate. The Co(II)-1 became the pentacoordinated complex by taking up an amine base in the axile site: Co(II)-1 + B ⇌ BCo(II)-1. For the mutual interaction of substituted pyridines with the Co(II)-1, the general behavior of the equilibrium constants was explained on the basis of the amine basicity and the Hammett equation by reference to the corresponding behavior of the porphyrin, corrin and corrole complexes. Moreover, there exists a systematic correlation between log K and the chemical shift of the corresponding 4-position in the 13C-NMR spectra of substituted pyridines. The isoequilibrium temperature obtained from a plot of Δ H against Δ S was 260 K. The equilibrium is primarily controlled by entropy at the usual temperature. The weaker coordination tendency of some hindered pyridine such as 2-methyl- and 2,6-dimethylpyridine toward Co(II)-1 was attributed to the steric effect between the in-plane ligand of Co(II)-1 and the 2- and/or 6-methyl groups of substituted pyridines in the coordination process.