Binuclear copper(II) complexes with N4O3 coordinating heptadentate ligand: synthesis, structure, magnetic properties, density-functional theory study, and catecholase activity

Inorganic Chemistry
Atanu BanerjeeKajal Krishna Rajak

Abstract

The N4O3 coordinating heptadentate ligand afforded binuclear complex [Cu 2(H 2L)(mu-OH)](ClO4)2 (1) and [Cu2(L)(H2O)2]PF6 (2). In complex 1, two copper ions are held together by mu-phenoxo and mu-hydroxo bridges, whereas in complex 2, the copper centers are connected only by a mu-phenoxo bridge. In 1, both the Cu(II) centers have square pyramidal geometry (tau=0.01-0.205), whereas in the case of 2, one Cu(II) center has square pyramidal (tau=0.2517) and other one has square based pyramidal distorted trigonal bipyramidal (tau=0.54) geometry. Complexes 1 and 2 show an strong intramolecular and very weak antiferromagnetic interaction, respectively. Density-functional theory calculations were performed to establish the magneto structural correlation between the two paramagnetic copper(II) centers. Both of the complexes display a couple of one-electron reductive responses near -0.80 and -1.10 V. The complexes show significant catalytic activity at pH 8.5 on the oxidation of 3,5-di- tert-butylcatechol (3,5-DTBC) to 3,5-di- tert-butylquinone (3,5-DTBQ), and the activity measured in terms of kcat=29-37 h(-1).

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Citations

Jun 22, 2013·Chemical Reviews·Scott E AllenMarisa C Kozlowski
Jan 1, 2009·Acta Crystallographica. Section E, Structure Reports Online·Jun Yang, Hong-Ji Chen
Jan 18, 2017·Chemistry : a European Journal·Jana GülzowAndreas Grohmann
Mar 15, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Yi-Hsueh HoJwu-Ting Chen
May 1, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Paramita KarAshutosh Ghosh
Jul 20, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Jaydeep AdhikaryDebasis Das
Nov 6, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Cristina NúñezCarlos Lodeiro
Jul 23, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Avijit SarkarDebashis Ray
Jan 25, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Aloke Kumar GhoshDebashis Ray
Jul 6, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·J A IsaacC Belle

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