Dinuclear copper(II) complexes: Solvent dependent catecholase activity

被引:38
作者
Banu, Kazi Sabnam [2 ]
Mukherjee, Madhuparna [2 ]
Guha, Averi [2 ]
Bhattacharya, Santanu [3 ]
Zangrando, Ennio [1 ]
Das, Debasis [2 ]
机构
[1] Univ Trieste, Dipartimento Sci Chim, I-34127 Trieste, Italy
[2] Univ Calcutta, Dept Chem, Kolkata 700009, India
[3] Maharaja Manindra Chandra Coll, Dept Chem, Kolkata 700003, India
关键词
Dinuclear Cu(II); Schiff-base; Catecholase activity; Solvent effect; BIMETALLIC OXIDATION CATALYSTS; SCHIFF-BASE LIGANDS; OXIDASE ACTIVITY; DICOPPER(II) COMPLEXES; CRYSTAL-STRUCTURES; SPECTROSCOPIC CHARACTERIZATION; REDOX PROPERTIES; MODEL COMPOUNDS; SERIES; DIOXYGEN;
D O I
10.1016/j.poly.2012.06.087
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Four new dicopper(II) complexes of phenol based compartmental ligands, namely [Cu-2((LH)-H-1)(2)(H2O)(2)(NO3)(2)] (NO3)(2) (1), [Cu-2(L-2)(OH)(H2O)(NO3)](NO3) (2), [Cu-2(L-3)(2)(H2O)(NO3)](NO3) (3) and [Cu-2(L-4)(H2O)(2)(NO3)] (NO3)(2) (4) [where L-1 = 2-formyl-4-methyl-6-(4-(aminomethyl)-piperidine)iminomethyl-phenolato, L-2 = 2,6-bis(2-amino-2-methyl-1-propanol)iminomethyl-4-methyl-phenolato, L-3 = 2-formy1-4-methyl-6-(benzylamine)iminomethyl-phenolato and L4 = 2,6-bis(2-aminoethylpyridine)iminomethyl-4-methyl-phenolato] have been synthesized and structurally characterized. The single crystal X-ray analyses reveal that all four complexes are dinuclear in nature; complexes 2 and 4 comprise of one respective ligand, whereas 1 and 3 are contain two respective ligands, and the Cu-Cu separation in each case is ca. 3.0 angstrom. All four complexes are soluble in dichloromethane (DCM), methanol, acetonitrile (ACN), dimethylsulfoxide (DMSO), water-methanol (50:50, v/v), and this property has been exploited to access the solvent effect on the catecholase activity of the complexes towards the aerobic oxidation of 3,5-DTBC to 3,5-DTBQ. A UV-Vis spectral study in the different solvents, followed by a kinetic investigation, suggests that the change in spectral behavior follows a similar trend, being dependent on the coordinating ability of the solvent, irrespective of the complex used. The commonly known physical parameters of the solvents, like the dielectric constant, dipole moment, polarity, etc., do not seem to be a key factor in controlling the catecholase activity. However, protic solvents are observed to be a better choice than aprotic solvents for the oxidation of 3,5-DTBC. (C) 2012 Elsevier Ltd. All rights reserved.
引用
收藏
页码:245 / 254
页数:10
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