Interplay between acetate ions, peripheral groups, and reactivity of the core nitrogens in transmetalation of tetrapyrroles

Chemistry : a European Journal
Lukasz OrzełGrazyna Stochel

Abstract

The mechanism of acetate-assisted transmetalation of tetrapyrroles was investigated in a model system consisting of chlorophyll a and copper(II) acetate in organic solvents by using a spectroscopic and kinetic approach. Surprisingly, acetate ions bind to the central Mg in chlorophyll much more strongly than do acetonitrile, methanol and even pyridine, one of the best ligands in chlorophyllic systems. This exceptionally strong non-symmetrical axial ligation of the central Mg by acetate causes its out-of-plane displacement and deformation of the tetrapyrrole ring, thus facilitating the interaction with an incoming CuII complex. This mechanism is controlled by a keto-enol tautomerism of the chlorophyll isocyclic ring. Additionally, depending on solvent, acetate activates the incoming metal ions. These new insights allow to suggest a mechanism for the acetate method of metal exchange in tetrapyrrolic macrocycles, which resembles biological insertion of metal ions into porphyrins. It also provides a guideline for the design of more efficient methods for the metalation of porphyrins and related macrocycles.

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Citations

Sep 22, 2011·Photochemistry and Photobiology·Nikolaos E IoannidisKiriakos Kotzabasis
Oct 14, 2008·Biochimica Et Biophysica Acta·Leszek FiedorGrazyna Stochel
Jun 24, 2017·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Ł OrzełL Fiedor
Jan 9, 2016·Spectrochimica Acta. Part A, Molecular and Biomolecular Spectroscopy·Darshna SharmaSuban K Sahoo
Feb 28, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Łukasz OrzełGrażyna Stochel
Jun 12, 2018·The Journal of Biological Chemistry·Benoît DesguinPatrice Soumillion
Dec 23, 2020·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Łukasz OrzełGrażyna Stochel
Aug 10, 2010·Inorganic Chemistry·Łukasz OrzełLeszek Fiedor
Aug 14, 2012·Journal of Chemical Theory and Computation·Dorota Rutkowska-Zbik, Tatiana Korona

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