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Coordination Complex of Cu(II) with Ligand Containing Carboxylic Acid Group: Synthesis, Characterization and Catecholase Activity
Corresponding Author(s) : Madhusudan Shit
Asian Journal of Chemistry,
Vol. 34 No. 8 (2022): Vol 34 Issue 8, 2022
Abstract
Present work reports the synthesis, characterization and catecholase like activity of a diaqua Cu(II) complex of type [(L2–)Cu(H2O)2] (1) with a tridentate ligand (E)-2-(3-hydroxy-3-phenyltriaz-1-en-1-yl)benzoic acid (LH2). Complex 1 is characterized by FT-IR, mass, EPR and UV-Vis spectroscopy. The isotropic hyperfine four line EPR spectrum of complex 1 in solution confirms the Cu(II) state in complex 1. The complex exhibits catalytic activity towards the oxidation of 3,5-di-tert. butyl catechol (3,5-DTBC) to 3,5-di-tert. butyl benzoquinone (3,5-DTBQ) with turnover number (Kcat) = 132.8 h-1 via formation of radical intermediate. The oxidation of 3,5-DTBC in presence of complex 1 is confirmed by the UV-Vis spectroscoy, mass spectra and EPR spectra. Complex 1 is EPR active in solution but the solution containing complex 1 and 3,5-di-tert. butyl catechol is EPR silent authenticating the formation of an organic radical in the catalytic oxidation process. In cyclic voltametry of complex 1, an irreversible cathodic peak appear at -0.19 V may be due to the Cu2+/Cu+ couple and an irreversible anodic wave appear at +1.35 V may be due to the oxidation of N3– to N3·-. Cyclic voltammetry of complex 1 with 3,5-DTBC gives a new anodic peak at +0.11 V, which is assigned as cat/sq·- redox couple [cat= 3,5-DTBC, sq·- = benzosemiquinonate anion radical].
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L.D. Raev, E. Voinova, I.C. Ivanov and D. Popov, Pharmazie, 45, 696 (1990).
A. Karaliota, O. Kretsi and C. Tzougraki, J. Inorg. Biochem., 84, 33 (2001); https://doi.org/10.1016/S0162-0134(00)00214-2
D. Egan, R. O’Kennedy, E. Moran, D. Cox, E. Prosser and R.D. Thornes, Drug Metab. Rev., 22, 503 (1990); https://doi.org/10.3109/03602539008991449
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B.B. Kumaar, V.J. Raju, V. Ranabaore and M.C. Ganorkar, Orient. J. Chem., 3, 34 (1987).
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E.I. Solomon, M.J. Baldwin and M.D. Lowery, Chem. Rev., 92, 521 (1992); https://doi.org/10.1021/cr00012a003
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R.H. Holm, P. Kennepohl and E.I. Solomon, Chem. Rev., 96, 2239 (1996); https://doi.org/10.1021/cr9500390
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N. Mohan, S.S. Sreejith and M.R.P. Kurup, Polyhedron, 173, 114129 (2019); https://doi.org/10.1016/j.poly.2019.114129
S.K. Dey and A. Mukherjee, New J. Chem., 38, 4985 (2014); https://doi.org/10.1039/C4NJ00715H
M. Shit, S. Maity, B. Biswas, P.K. Mudi, T. Weyhermüller and P. Ghosh, New J. Chem., 45, 2221 (2021); https://doi.org/10.1039/D0NJ05238H
M. Mondal, S. Ghosh, S. Maity, S. Giri and A. Ghosh, Inorg. Chem. Front., 7, 247 (2020); https://doi.org/10.1039/C9QI00975B
J. Mukherjee and R. Mukherjee, Inorg. Chim. Acta, 337, 429 (2002); https://doi.org/10.1016/S0020-1693(02)01106-4
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S.C. Saha and S. Maji, Indian J. Chem. A, 29A, 573 (1990).
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