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Structure and Coordination Determination of Peptide-metal Complexes Using 1D and 2D 1H NMR
Published on: December 16, 2013
Four-Coordinate Copper Halonitrosyl {CuNO}10 Complexes
Jamey K Bower1, Alexander Yu Sokolov1, Shiyu Zhang1
1Department of Chemistry and Biochemistry, The Ohio State University, 100 W. 18th Ave, Columbus, OH, USA.
Abstract:
While copper nitrosyl complexes are implicated in numerous biological systems, isolable examples remain limited. In this report, we show that [Cl3 CuNO]- , with a {CuNO}10 electron configuration, can be generated by nitrite reduction at a copper(I) dichloride anion or by nitric oxide addition to a copper(II) trichloride precursor. The bromide analogue, [Br3 CuNO]- was synthesized analogously, and both copper halonitrosyl complexes were characterized by X-ray diffraction and a variety of spectroscopic methods. Experimental data and multireference (CASSCF/NEVPT2) calculations provide strong evidence for a CuII -NO. ground state. Both [Cl3 CuNO]- and [Br3 CuNO]- release and recapture NO. reversibly, and exhibit nitrosative reactivities toward a wide range of biological nucleophiles, such as amines, alcohols, and thiols.
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