Structural and Spectroscopic Characterization of Mononuclear Copper(I) Nitrosyl Complexes:  End-on versus Side-on Coordination of NO to Copper(I)

• Published in: Journal of the American Chemical Society Vol. 130; no. 4; pp. 1205 - 1213
• Main Authors: Fujisawa, Kiyoshi, Tateda, Akira, Miyashita, Yoshitaro, Okamoto, Ken-ichi, Paulat, Florian, Praneeth, V. K. K, Merkle, Anna, Lehnert, Nicolai
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 30.01.2008
• Subjects: Biochemistry - methods; Cations; Copper - chemistry; Crystallography, X-Ray; Electron Spin Resonance Spectroscopy; Electronics; Ligands; Models, Chemical; Molecular Conformation; Molecular Structure; Nitric Oxide - chemistry; Nitrite Reductases - chemistry; Spectrophotometry - methods; Spectrophotometry, Ultraviolet - methods
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja075071d

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 ν(N−O) at 1698 cm-1 and ν(Cu−NO) split at 365/338 cm-1 for 1, which translates to force constants of 12.53 (N−O) and 1.31 mdyn/Å (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 ν(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 ∥(g z ) and the Cu−N−O angle is established. Finally, high-quality MCD spectra of 1 are presented and assigned using TD-DFT calculations. Based on the in-depth spectroscopic characterization of end-on bound NO to copper(I) presented in this work, it is possible to determine the binding mode of the Cu−NO intermediate of Cu nitrite reductase studied by Scholes and co-workers (Usov, O. M.; Sun, Y.; Grigoryants, V. M.; Shapleigh, J. P.; Scholes, C. P., J. Am. Chem. Soc. 2006, 128, 13102−13111) in solution as strongly bent (∼135°) but likely not side-on.