Structural and spectroscopic characterization of mononuclear copper(I) nitrosyl complexes: end-on versus side-on coordination of NO to copper(I)

Journal of the American Chemical Society
Kiyoshi FujisawaNicolai Lehnert

Abstract

Two crystal structures of the mononuclear copper(I)-nitrosyl complexes [Cu(L3)(NO)] (1) and [Cu(L3')(NO)](ClO4) (2) with the related coligands L3- (hydrotris(3-tert-butyl-5-isopropyl-1-pyrazolyl)borate) and L3' (tris(3-tert-butyl-5-isopropyl-1-pyrazolyl)methane) are presented. These compounds are then investigated in detail using a variety of spectroscopic methods. Vibrational spectra show nu(N-O) at 1698 cm(-1) and nu(Cu-NO) split at 365/338 cm(-1) for 1, which translates to force constants of 12.53 (N-O) and 1.31 mdyn/A (Cu-NO), respectively. The weak Cu-NO force constant is in agreement with the observed instability of the Cu-NO bond. Interestingly, complex 2 with the neutral coligand L3' shows a stronger N-O bond, evident from nu(N-O) at 1742 cm(-1). This difference is attributed to a true second coordination sphere effect, where the covalency of the Cu(I)-NO bond is not altered. The EPR spectrum of 1 is in agreement with the Cu(I)-NO(radical) electronic structure of the complexes, as obtained from density functional theory (DFT) calculations. In addition, an interesting trend between g parallel(gz) and the Cu-N-O angle is established. Finally, high-quality MCD spectra of 1 are presented and assigned using TD-DFT calculatio...Continue Reading

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Citations

Aug 8, 2009·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Ga Young ParkKenneth D Karlin
Aug 14, 2010·Inorganic Chemistry·Lindsey E McQuadeStephen J Lippard
Dec 15, 2015·Biochemistry·Masami Lintuluoto, Juha M Lintuluoto
Mar 2, 2016·Proceedings of the National Academy of Sciences of the United States of America·Yohta FukudaEiichi Mizohata
Mar 31, 2016·Journal of the American Chemical Society·Davide LionettiTheodor Agapie
Jun 22, 2016·Nature Chemistry·Shiyu ZhangTimothy H Warren
Jun 29, 2016·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Shoko SomaKiyoshi Fujisawa
Jan 18, 2017·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Kiyoshi Fujisawa
Apr 4, 2014·Chemical Reviews·Luisa B Maia, José J G Moura
Jul 14, 2017·Metallomics : Integrated Biometal Science·Sam HorrellMichael A Hough
Jul 28, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Kiyoshi FujisawaNicolai Lehnert
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