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Issue 14, 2017
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Hydroxide-bridged dicopper complexes: the influence of secondary coordination sphere on structure and catecholase activity

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Abstract

Amide-based ligands (H2L1–6) with assorted functional groups appended to them have been used for the synthesis of dicopper(II) complexes 1–6 having a Cu(μ-OH)Cu core. The crystal structures of 1–6 show that while every Cu(II) ion is ligated within the N3 pincer cavity of a potentially multidentate ligand, two Cu(II) centers are bridged by a hydroxide group. Notably, the Cu(μ-OH)Cu core is encased within the secondary coordination sphere intricately created by the appended groups. While complexes 1 and 2 exhibit the presence of an H-bond acceptor in the proximity of the Cu(μ-OH)Cu core, complexes 3 and 4 display the occurrence of both the H-bond donor as well as H-bond acceptor groups in the vicinity of the Cu(μ-OH)Cu core. In contrast, complexes 5 and 6 present modified secondary coordination spheres around the Cu(μ-OH)Cu core with limited H-bonding interacting groups in 5 and no such groups in 6. We show that the extent of H-bonding by the appended groups modulates not only the Cu–OH bond distance, Cu(μ-OH)Cu angle and Cu–Cu separation but also the Cu2+/Cu+ redox potential. All six complexes were utilized for their ability to oxidize 3,5-di-tert-butylcatechol, and the catecholase activity results have been correlated to the secondary coordination sphere created by the appended groups in all six complexes.

Graphical abstract: Hydroxide-bridged dicopper complexes: the influence of secondary coordination sphere on structure and catecholase activity

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Publication details

The article was received on 24 Dec 2016, accepted on 10 Mar 2017 and first published on 10 Mar 2017


Article type: Paper
DOI: 10.1039/C6DT04858G
Citation: Dalton Trans., 2017,46, 4617-4627
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    Hydroxide-bridged dicopper complexes: the influence of secondary coordination sphere on structure and catecholase activity

    D. Bansal and R. Gupta, Dalton Trans., 2017, 46, 4617
    DOI: 10.1039/C6DT04858G

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