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.
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