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Vol. 27 No. 12 (2015): Vol 27 Issue 12

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Solvent Dependent Disproportionation of Cu(II) Complexes of N2O2-Type Ligands: Direct Evidence of Formation of Phenoxyl Radical: An Experimental and Computational Study

https://doi.org/10.14233/ajchem.2015.19193
Rajib Kumar Debnath
Department of Chemistry, Gauhati University, Guwahati-781 014, India
Apurba Kalita
Department of Chemistry, Indian Institute of Technology Guwahati, Guwahati-781 039, India
Sourab Sinha
Department of Chemistry, Arya Vidyapeeth College, Guwahati-781 016, India
Pradip Kr. Bhattacharyya
Department of Chemistry, Arya Vidyapeeth College, Guwahati-781 016, India
Biplab Mondal
Department of Chemistry, Indian Institute of Technology Guwahati, Guwahati-781 039, India
Jatindra Nath Ganguli
Department of Chemistry, Gauhati University, Guwahati-781 014, India

Corresponding Author(s) : Jatindra Nath Ganguli

jatin_ganguli_gu@yahoo.co.in

Asian Journal of Chemistry, Vol. 27 No. 12 (2015): Vol 27 Issue 12

Abstract

Four Cu(II) complexes (1, 2, 3 and 4) with N2O2-type ligand, H2L1, H2L2, H2L3 and H2L4, respectively have been synthesized as the functional model for galactose oxidase. In presence of acetonitrile the Cu(II) centres in the complexes, undergo reduction with simultaneous oxidation of the ligands. The ligand oxidized products are isolated and characterized. Spectroscopic studies indicate that this disproportionation goes through the formation of a Cu(II)-phenoxyl intermediate. The complexes also undergoes the same reaction with pyridine, which indicates the involvement of the exergonic N-donor ligand for the formation of Cu(II)-phenoxyl complex. The Cu(II)-phenoxyl complexes are found to be stable in methanol in presence of a strong base. The paramagnetic centers in the Cu(II)-phenoxyl complexes were found to be weakly ferromagnetically coupled. The complexes, in acetonitrile solvent, have been found to oxidize primary alcohols to corresponding aldehydes. In absence of single crystal structures of the complexes, we optimized the structures using density functional theory (DFT). The UV-visible peaks of complexes as found from time dependent density functional theory (TDDFT) calculations match well with the observed experimental results.

Keywords

Galactose oxidase N2O2 type ligands Phenoxyl radical DFT study
Kumar Debnath, R., Kalita, A., Sinha, S., Kr. Bhattacharyya, P., Mondal, B., & Nath Ganguli, J. (2015). Solvent Dependent Disproportionation of Cu(II) Complexes of N2O2-Type Ligands: Direct Evidence of Formation of Phenoxyl Radical: An Experimental and Computational Study. Asian Journal of Chemistry, 27(12), 4490–4500. https://doi.org/10.14233/ajchem.2015.19193
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