Detailed spectroscopic, thermodynamic, and kinetic characterization of nickel(II) complexes with 2,2′-bipyridine and 1,10-phenanthroline attained via equilibrium-restricted factor analysis

The molar absorptivity curves of the mono and bis nickel(II) complexes of 2,2'-bipyridine and 1,10-phenanthroline have been deduced from the composite absorbance data of a series of equilibrium solutions in methanol using equilibrium-restricted factor analysis, a technique for extracting spectral and thermodynamic information for component species involved in solution equilibria. The solutions achieve equilibrium slowly (t(1/2) approximate to 100 min) as the amounts of the tris and methanolato complexes are initially in excess. The relative formation constants at 293 K have been determined with a high degree of accuracy, especially for the bipyridine complexes: log(K-1/K-2) = 0.340(4) and log(K-2/K-3) = 1.091(6). Solubility limitations compromised the accuracy of the thermodynamic results for the phenanthroline complexes.