Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 135, Issue 45, Pages 16746-16749Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja406476y
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- Direct For Mathematical & Physical Scien
- Division Of Chemistry [0957606] Funding Source: National Science Foundation
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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 (BuSNO)-Bu-t leads to formation of (iPr2)TpCu(NO) and the unsymmetrical disulfide RS-(SBu)-Bu-t. Quantum mechanical investigations with B3LYP-D3/6-311G(d) suggest formation of a kappa(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 (iPr)2TpCu-SC6F5 and 2 equiv NO, we outline a new, detailed catalytic cycle for NO generation from RSNOs at Cu.
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