Mechanistic Information on CuII Metalation and Transmetalation of Chlorophylls

Chlorophyll a and pheophytin a have been treated with various metal salts in solution. As a result, metallo derivatives of photosynthetic pigments were formed, or the chlorine ring was oxidized. These studies showed that both effects can be caused by Cu-II ions depending on the redox potential of its complexes formed in specific media. In this report the results of studies on metal insertion and exchange reactions are presented. According to the common use of the acetate method in the synthesis of metallotetrapyrroles, and the fact that acetates coordinated to Cu-II ions protect chlorophylls from oxidative degradation, Cu-II acetate monohydrate was selected as main reagent. The metalation and transmetalation processes were investigated with spectroscopic (UV/Vis absorption and emission) and kinetic (conventional and high-pressure) techniques. It turned out that differences in solvent properties can significantly affect not only the rates (metalation), but also the course (transmetalation) of the reaction. The most pronounced effect was found for the transmetalation reaction in acetonitrile, which was terminated at the very initial stage. As shown elsewhere, some special agents/factors, such as excess of acetate, are required to facilitate the dissociation of Mg2+ and to push the reaction forward towards formation of the Cu-II derivative of chlorophyll. The mechanisms of two other reactions are proposed on the basis of the determined activation parameters, which correspond to the general mechanisms for metalation and transmetalation of tetrapyrroles with sitting-atop and bimetallic intermediates, respectively. The bimetallic complex of chlorophyll in methanol is probably the most stable complex of this type observed ever. It confirms that spontaneous exchange of Mg2+ by Cu-II occurring in plants must result from specific conditions and/or involve contribution from other components of the photosystem. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)