Nitric Oxide Release from a Nickel Nitrosyl Complex Induced by One-Electron Oxidation

Reaction of [Ni(NO)(bipy)][PF6] (2) with AgPF6 or [NO][PF6] in MeCN results in formation of [Ni(bipy)(x)(MeCN)(y)](2+). and release of NO gas in moderate yields. In contrast, the addition of the inner sphere oxidant Ph2S2 to 2 does not result in denitrosylation. Instead, the diphenyldisulfide adduct [{(bipy)(NO)Ni}2(mu-S2Ph2)][PF6](2) (3) is formed in good yield. However, oxidation of 2 with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) does results in cleavage of the Ni-NO bond and generation of NO. The metal-containing product, [(bipy)Ni(eta(2)-TEMPO)] [PF6] (4), can be isolated as an orange-brown solid in excellent yields. In the solid state, complex 4 contains a side-on bound TEMPO- ligand, which is characterized by a long N-O bond length [1.383(2) angstrom]. The contrasting reactivity of Ph2S2 and TEMPO likely relates to their different redox potentials, as Ph2S2 is a relatively weak oxidant. Finally, the addition of pyridine-N-oxide to 2 results in the formation of the adduct, [(bipy)Ni(NO)(ONC5H5)][PF6] (5). No evidence of NO release is observed in this reaction, probably because of the low one-electron (1e(-)) reduction potential of pyridine-N-oxide.