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Issue 16, 2013
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Nitric oxide reactivity of Cu(II) complexes of tetra- and pentadentate ligands: structural influence in deciding the reduction pathway

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Abstract

Four Cu(II) complexes, 1, 2, 3 and 4, are synthesized with ligands, L11, L22, L33 and L44 [L11 = N1,N2-bis((pyridin-2-yl)methyl)ethane-1,2-diamine; L22 = N1,N3-bis((pyridin-2-yl)methyl)propane-1,3-diamine; L33 = N1,N1,N2-tris((pyridin-2-yl)methyl)ethane-1,2-diamine; L44 = N1-((1-methyl-1H-imidazol-2-yl)methyl)-N1,N2-bis((pyridin-2-yl)methyl)ethane-1,2-diamine], respectively, as their perchlorate salts. The complexes were characterized by various spectroscopic techniques as well as single crystal X-ray structure determination. Nitric oxide reactivities of the complexes were studied in acetonitrile as well as methanol solvent. It has been found that the ligand frameworks have a considerable effect in controlling the mechanism of the reduction of a Cu(II) center by nitric oxide. The flexibility of the ligand/s for a Cu(II) complex to attain a trigonal bipyramidal geometry after NO coordination is found to be the most important parameter in dictating the pathway for their interaction. In the present study, all the four compounds, because of structural constraints, were found to follow a deprotonation pathway for the reduction of a Cu(II) center by nitric oxide rather than [CuII–NO] intermediate formation. All the ligands were found to yield an N-nitrosoamine product along with the reduction of Cu(II) centers by nitric oxide.

Graphical abstract: Nitric oxide reactivity of Cu(ii) complexes of tetra- and pentadentate ligands: structural influence in deciding the reduction pathway

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Publication details

The article was received on 11 Sep 2012, accepted on 04 Feb 2013 and first published on 28 Feb 2013


Article type: Paper
DOI: 10.1039/C3DT32580F
Citation: Dalton Trans., 2013,42, 5731-5739
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    Nitric oxide reactivity of Cu(II) complexes of tetra- and pentadentate ligands: structural influence in deciding the reduction pathway

    P. Kumar, A. Kalita and B. Mondal, Dalton Trans., 2013, 42, 5731
    DOI: 10.1039/C3DT32580F

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