查看文章

Reaction of [Ni(NO)(bipy)(Me₂phen)][PF₆] with 1 equiv of nitric oxide (NO) in CH₂Cl₂ results in the formation of N₂O and [{(Me₂phen)Ni(NO)}₂(μ–η¹-N:η¹-O)-NO₂)][PF₆] (3), along with the known complex, [Ni(bipy)₃][PF₆]₂ (4). The isolation of complex 3, which contains a nitrite ligand, demonstrates that the reaction of [Ni(NO)(bipy)(Me₂phen)][PF₆] with exogenous NO results in NO disproportionation and not NO reduction. Complex 3 could also be accessed by reaction of [Ni(NO)(Me₂phen)][PF₆] (5) with (Me₂phen)Ni(NO)(NO₂) (7) in good yield. Complexes 3, 5, and 7 were fully characterized, including analysis by X-ray crystallography in the case of 3 and 7. Furthermore, addition of 0.5 equiv of bipy to [Ni(NO)(bipy)][PF₆] results in formation of the hyponitrite complex, [{(bipy)Ni(κ²-O₂N₂)}η¹:η¹-N,N-{Ni(NO)(bipy)}₂][PF₆]₂ (9), in modest yield. Importantly, the hyponitrite ligand in 9 is thought to form via coupling of two …