Spectrophotometric determination of the formation constants of calcium(II) complexes with 2,2'-bipyridyl and 1,10-phenanthroline in acetonitrile

Abstract

The oxygen-evolving complex (OEC), which consists of a calcium-manganese cluster, is the reaction center of the Photosystem II. At this catalytic site, the water-splitting reaction in dioxygen and hydronium ions occurs. In order to partially reproduce the water splitting process, several studies have reported the synthesis of functional model complexes. Nevertheless, there is a small amount of reports, concerning the spectral behavior of calcium complexes or the calcium role in the cluster. In this work, in order to explore the absorption spectrum of calcium species in acetonitrile, an equilibrium study of the calcium complexes with 2,2'-bipyridyl or 1,10-phenanthroline, was carried out. The formation constants and the calculated electronic spectrum of each complex was obtained by a modified method of continuous variations consisting in a correlation of the experimental spectrophotometric data with the HypSpec software. The values of the formation constants for the calcium(II) complexes with 2,2'-bipyridyl and 1,10-phenanthroline, are Log β110 = 4.39 ± 0.02 and Log β110 = 5.94 ± 0.05, respectively.