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Issue 31, 2012
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Nitric oxide reactivity of copper(ii) complexes of bidentate amineligands: effect of chelate ring size on the stability of a [CuII–NO] intermediate

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Abstract

Three copper(II) complexes, 1, 2, and 3 with L11, L22 and L33 [L11 = 2-(2-aminoethyl)-pyridine; L2 = 2-(N-ethyl-2-aminoethyl)-pyridine; L33 = 3,3′-iminobis(N,N-dimethylpropylamine)], respectively, were synthesized and characterized. Addition of nitric oxide gas to the degassed acetonitrile solution of the complexes were found to result in the reduction of the copper(II) center to copper(I). In cases of complexes 1 and 2, the formation of the [CuII–NO] intermediate prior to the reduction of Cu(II) was evidenced by UV-visible, solution FT-IR and X-band EPR spectroscopic studies. However, for complex 3, the formation of [CuII–NO] has not been observed. DFT calculations on the [CuII–NO] intermediate generated from complex 1 suggest a distorted square pyramidal geometry with the NO ligand coordinated to the CuII center at an equatorial site in a bent geometry. In the case of complex 1, the reduction of the copper(II) center by nitric oxide afforded ligand transformation through diazotization at the primary amine site in acetonitrile solution; whereas, in an acetonitrile–water mixture, it resulted in 2-(pyridine-2-yl)ethanol. On the other hand, in cases of complexes 2 and 3, it was found to yield N-nitrosation at the secondary amine site in the ligand frameworks. The final organic products, in each case, were isolated and characterized by various spectroscopic studies.

Graphical abstract: Nitric oxide reactivity of copper(ii) complexes of bidentate amine ligands: effect of chelate ring size on the stability of a [CuII–NO] intermediate

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Supplementary files

Article information


Submitted
24 Jan 2012
Accepted
14 May 2012
First published
04 Jul 2012

Dalton Trans., 2012,41, 9543-9552
Article type
Paper

Nitric oxide reactivity of copper(II) complexes of bidentate amine ligands: effect of chelate ring size on the stability of a [CuII–NO] intermediate

M. Sarma, V. Kumar, A. Kalita, R. C. Deka and B. Mondal, Dalton Trans., 2012, 41, 9543
DOI: 10.1039/C2DT30721A

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