Coordinatively Unsaturated Nickel Nitroxyl Complex: Structure, Physicochemical Properties, and Reactivity toward Dioxygen.

For its important roles in biology, nitrogen monoxide (·NO) has become one of the most studied and fascinating molecules in chemistry. ·NO itself acts as a "noninnocent" or "redox active" ligand to transition metal ions to give metal-NO (M-NO) complexes. Because of this uncertainty due to redox chemistry, the real description of the electronic structure of the M-NO unit requires extensive spectroscopic and theoretical studies. We previously reported the Ni-NO complex with a hindered N3 type ligand [Ni(NO)(L3)] (L3 - denotes hydrotris(3-tertiary butyl-5-isopropyl-1-pyrazolyl)borate anion), which contains a high-spin (hs) nickel(II) center and a coordinated 3 NO - . This complex is very stable toward dioxygen due to steric protection of the nickel(II) center. Here, we report the dioxygen reactivity of a new Ni-NO complex, [Ni(NO)(I)(L1″)] , with a less hindered N2 type bis(pyrazolyl)methane ligand, which creates a coordinatively unsaturated ligand environment about the nickel center. Here, L1″ denotes bis(3,5-diisopropyl-1-pyrazolyl)methane. This complex is also described as a hs-nickel(II) center with a bound 3 NO - , based on spectroscopic and theoretical studies. Unexpectedly, the reaction of [Ni(NO)(I)(L1″)] with O 2 yielded [Ni(κ 2 -O 2 N)(L1″) 2 ](I 3 ) , with the oxidation of both 3 NO - and the I - ion to yield NO 2 - and I 3 - . Both complexes were characterized by X-ray crystallography, IR, and UV-Vis spectroscopy and theoretical calculations.