Abstract
The 16-membered modified [N6] macrocylic ligand (L), a mimic to cyclic, hexapeptide is reacted with MCl2 and MCl3 resulting in complexes with stoichiometrices [MLCl2] (M = Cr, Mn, Co, Ni, Cu), [MLCl3] (M = Pt, Pd) and [MLCl2]Cl (M = Fe, Ru). Its reactions with the precursors [M(Ph3P)2Cl2] (M = Co, Ni, Pt, Pd) follow a ligand displacement path affording the final products which do not contain coordinated Ph3P. Complexes have been characterized from results of elemental analyses, conductometric, magnetic susceptibility, i.r. and u.v.–vis (ligand field) spectral studies. Magnetic susceptibility and ligand field spectral data are consistent with a hexacoordinate geometry for Cr2+, Mn2+, Fe3+, Co2+, Ni2+ and Cu2+ and four coordinate square-planar geometry for Pt2+ and Pd2+. Molecular orbital computations using CSChem ultra MOPAC software for an optimized minimum energy plot of the structure shows that the ligand binds metal ions as a tetradentate (N,N,N,N) chelating agent. Cyclic voltammetric studies indicate formation of stable reversible or quasi-reversible redox couples in solutions, which corroborates a kinetic stability of these complexes in their variable oxidation states.
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