Transformation of Formazanate at Nickel(II) Centers to Give a Singly Reduced Nickel Complex with Azoiminate Radical Ligands and Its Reactivity toward Dioxygen.

The heteroleptic (formazanato)nickel bromide complex LNi(μ-Br)2NiL [LH = Mes-NH-N═C(p-tol)-N═N-Mes] has been prepared by deprotonation of LH with NaH followed by reaction with NiBr2(dme). Treatment of this complex with KC8 led to transformation of the formazanate into azoiminate ligands via N-N bond cleavage and the simultaneous release of aniline. At the same time, the potentially resulting intermediate complex L'2Ni [L' = HN═C(p-tol)-N═N-Mes] was reduced by one additional electron, which is delocalized across the π system and the metal center. The resulting reduced complex [L'2Ni]K(18-c-6) has a S = 1/2 ground state and a square-planar structure. It reacts with dioxygen via one-electron oxidation to give the complex L'2Ni, and the formation of superoxide was detected spectroscopically. If oxidizable substrates are present during this process, these are oxygenated/oxidized. Triphenylphosphine is converted to phosphine oxide, and hydrogen atoms are abstracted from TEMPO-H and phenols. In the case of cyclohexene, autoxidations are triggered, leading to the typical radical-chain-derived products of cyclohexene.