Structural and Spectroscopic Characterization of Mononuclear Copper(l) Nitrosyl Complexes: End-on versus Side-on Coordination of NO to Copper(l).
Two crystal structures of the mononuclear copper(l)-nitrosyl complexes [Cu(L3)(NO)] (1) and [Cu(L3′)(NO)](ClO) (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 the...
| Publicado en: | Journal of the American Chemical Society Vol. 130; no. 4; pp. 1205 - 1214 |
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| Autores principales: | , , , , , , , |
| Formato: | Artículo |
| Publicado: |
American Chemical Society
1/30/2008
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| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=29436575&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 29436575 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 1/30/2008 vid: 130 iid: 4 pid: 997 pub: American Chemical Society artinfo: ui: 29436575 10.1021/ja075071d ppf: 1205 ppct: 9 formats: tig: atl: Structural and Spectroscopic Characterization of Mononuclear Copper(l) Nitrosyl Complexes: End-on versus Side-on Coordination of NO to Copper(l). aug: au: Fujisawa, Kiyoshi Tateda, Akira Miyashita, Yoshitaro Okamoto, Ken-Ichi Paulat, Florian Praneeth, V. K. K. Merkle, Anna Lehnert, Nicolai affil: University of Tsukuba University of Michigan su: Mononucleosis Molecular spectroscopy Electronic structure Density functionals Electronic systems Electronic circuit design sug: subj: Mononucleosis Molecular spectroscopy Electronic structure Density functionals Electronic systems Electronic circuit design ab: Two crystal structures of the mononuclear copper(l)-nitrosyl complexes [Cu(L3)(NO)] (1) and [Cu(L3′)(NO)](ClO) (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 v(N—O) at 1698 cm and v(Cu—NO) split at 365/338 cm 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 v(N—O) at 1742 cm. This difference is attributed to a true second coordination sphere effect, where the covalency of the Cu(l)—NO bond is not altered. The EPR spectrum of 1 is in agreement with the Cu(l)—NO(radical) electronic structure of the complexes, as obtained from density functional theory (DFT) calculations. In addition, an interesting trend between g(g) 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(l) 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, 0. 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. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2008 holdings: @attributes: islocal: N |
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