NDLI: Fine tuning of copper(II)–chlorophyll interactions in organic media. Metalation versus oxidation of the macrocycle

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Stochel, Grazyna Rutkowska-zbik, Dorota Orzel, Lukasz Fiedor, Leszek Szmyd, Bartlomiej Van Eldik, Rudi
Description	Author Affiliation: Orzel L ( Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Kraków, Poland. orzel@chemia.uj.edu.pl.)
Abstract	The nature of chlorophyll interactions with copper(II) ions varies considerably in organic solvents, depending on the dominant coordinative form. Besides formation of the metallo tetrapyrrolic complex, Cu(II) ions can cause oxidation of the pigment, reversible or irreversible, which can lead to the destruction of the macrocyclic structure. All these reaction types can be distinguished within a quite narrow range of reaction conditions. The ability to form new metallo derivatives in either metalation or transmetalation reactions is obviously limited by the concentration of the potential oxidant, but can be secured below this level via suitable composition of the reaction system. The decisive factor in the selection of a specific reaction pathway is the presence of a potential ligand that can affect the reactivity of Cu(II) for example by shifting its redox potential. Spectroscopic and electrochemical studies were performed in order to determine the predominant species of Cu(II) in methanol, nitromethane and acetonitrile in the presence of chloride and acetate ions, as well as to assign their appropriate oxidizing ability. This allowed us to estimate the boundary conditions for the electron transfer processes in chlorophyll–Cu(II) systems. Chlorophyll and its free base can undergo both types of electron transfer processes, however, they reveal different susceptibilities that make this class of ligands quite versatile markers in tuning the reactivity of metal ions in solutions.
ISSN	14779226
Issue Number	13
Volume Number	44
e-ISSN	13645447
Journal	Dalton Trans.
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2015-04-07
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chlorophyllides Chemistry Coordination Complexes Copper Methane Solvents Molecular Structure Oxidation-Reduction Journal Article Research Support, Non-U.S. Gov't
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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