Synthesis, crystal structures and electrochemical characterization of dinuclear paddlewheel copper(II) carboxylates

M Iqbal; Saqib Ali; N Muhammad; Manzar Sohail

doi:10.1016/j.poly.2013.04.020

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Synthesis, crystal structures and electrochemical characterization of dinuclear paddlewheel copper(II) carboxylates

Journal article

Peer reviewed

Synthesis, crystal structures and electrochemical characterization of dinuclear paddlewheel copper(II) carboxylates

M Iqbal, Saqib Ali, N Muhammad and Manzar Sohail

Polyhedron, Vol.57, pp.83-93

2013

DOI: https://doi.org/10.1016/j.poly.2013.04.020

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Abstract

dinuclear Cu(II) complexes

crystal structures

heterogeneous kinetics

Two new dinuclear copper(II) complexes 1 and 2, viz., [pyCu(μ2-OOCCH2C6H4R)4Cupy] where R = para-NO2(1) and para-CH3(2) and py = pyridine, have been synthesized and characterized using FT-IR, single crystal XRD and electrochemical solution studies. In both complexes, the two copper centers are linked by four carboxylate ligands in bridging bidentate bonding fashion. Each copper(II) ion is penta-coordinated with distorted square pyramidal geometry. Both complexes have typical paddlewheel structures with the apical positions occupied by pyridine molecules. The electrochemical behavior of the complexes was investigated by cyclic voltammetry in which the complexes gave rise to metal centered single electron irreversible electro-activity, corresponding to Cu(II)/Cu(III) oxidation and Cu(II)/Cu(I) reduction processes. A reduction wave in relatively higher negative potential range (-1.3 to -1.4 V) was observed for the nitro group of complex 1. From the slope value of log I versus -log v, the redox processes were found predominantly diffusion controlled. The order of diffusion coefficient and heterogeneous rate constant for oxidation is: 1 > 2 owing to the more stable redox products in case of 1 while for reduction the order is: 2 > 1 due to overriding solvent effects and the larger molecular mass of 1 compared to 2. The charge transfer coefficient was also calculated and found typical of the irreversible redox processes.

Details

Title: Synthesis, crystal structures and electrochemical characterization of dinuclear paddlewheel copper(II) carboxylates
Authors: M Iqbal (Author) - Quaid-i-Azam University, Pakistan
Saqib Ali (Author) - Quaid-i-Azam University, Pakistan
N Muhammad (Author) - Abdul Wali Khan University, Pakistan
Manzar Sohail (Author) - University of the Sunshine Coast
Publication details: Polyhedron, Vol.57, pp.83-93
Publisher: Pergamon
Date published: 2013
DOI: 10.1016/j.poly.2013.04.020
ISSN: 0277-5387
Organisation Unit: School of Science and Engineering - Legacy; University of the Sunshine Coast, Queensland
Language: English
Record Identifier: 99448645302621
Output Type: Journal article

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Collaboration types: Domestic collaboration; International collaboration
Web Of Science research areas: Chemistry, Inorganic & Nuclear; Crystallography

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