دورية أكاديمية
Copper(I) nitrosyls from reaction of copper(II) thiolates with S-nitrosothiols: mechanism of NO release from RSNOs at Cu.
| العنوان: | Copper(I) nitrosyls from reaction of copper(II) thiolates with S-nitrosothiols: mechanism of NO release from RSNOs at Cu. |
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| المؤلفون: | Zhang S; Department of Chemistry, Georgetown University , Box 571227-1227, Washington, DC 20057, United States., Çelebi-Ölçüm N, Melzer MM, Houk KN, Warren TH |
| المصدر: | Journal of the American Chemical Society [J Am Chem Soc] 2013 Nov 13; Vol. 135 (45), pp. 16746-9. Date of Electronic Publication: 2013 Oct 29. |
| نوع المنشور: | Journal Article; Research Support, U.S. Gov't, Non-P.H.S. |
| اللغة: | English |
| بيانات الدورية: | Publisher: American Chemical Society Country of Publication: United States NLM ID: 7503056 Publication Model: Print-Electronic Cited Medium: Internet ISSN: 1520-5126 (Electronic) Linking ISSN: 00027863 NLM ISO Abbreviation: J Am Chem Soc Subsets: MEDLINE |
| أسماء مطبوعة: | Publication: Washington, DC : American Chemical Society Original Publication: Easton, Pa. [etc.] |
| مواضيع طبية MeSH: | Copper/*chemistry , Free Radical Scavengers/*administration & dosage , Nitric Oxide/*administration & dosage , S-Nitrosothiols/*chemistry , Sulfhydryl Compounds/*chemistry, Catalysis ; Free Radical Scavengers/chemistry ; Models, Molecular ; Nitric Oxide/chemistry |
| مستخلص: | S-nitrosothiols (RSNOs) serve as ready sources of biological nitric oxide activity, especially in conjunction with copper centers. We report a novel pathway for the generation of NO within the coordination sphere of copper model complexes from reaction of copper(II) thiolates with S-nitrosothiols. Reaction of tris(pyrazolyl)borate copper(II) thiolates (iPr2)TpCu-SR (R = C6F5 or CPh3) with (t)BuSNO leads to formation of (iPr2)TpCu(NO) and the unsymmetrical disulfide RS-S(t)Bu. Quantum mechanical investigations with B3LYP-D3/6-311G(d) suggest formation of a κ(1)-N-RSNO adduct (iPr2)TpCu(SR)(R'SNO) that precedes release of RSSR' to deliver (iPr2)TpCu(NO). This process is reversible; reaction of (iPr2)TpCu(NO) (but not (iPr2)TpCu(NCMe)) with C6F5S-SC6F5 forms (iPr2)TpCu-SC6F5. Coupled with the facile, reversible reaction between (iPr2)TpCu(NO) and C6F5SNO to give (iPr2)TpCu-SC6F5 and 2 equiv NO, we outline a new, detailed catalytic cycle for NO generation from RSNOs at Cu. |
| المشرفين على المادة: | 0 (Free Radical Scavengers) 0 (S-Nitrosothiols) 0 (Sulfhydryl Compounds) 31C4KY9ESH (Nitric Oxide) 789U1901C5 (Copper) |
| تواريخ الأحداث: | Date Created: 20131012 Date Completed: 20140617 Latest Revision: 20131113 |
| رمز التحديث: | 20231215 |
| DOI: | 10.1021/ja406476y |
| PMID: | 24111922 |
| قاعدة البيانات: | MEDLINE |
Find this issue from the American Chemical Society | تدمد: | 1520-5126 |
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| DOI: | 10.1021/ja406476y |