Reductive Cleavage of <i>O</i>-, <i>S</i>-, and <i>N</i>-Organonitroso Compounds by Nickel(I) β-Diketiminates

An electron-rich nickel(I) β-diketiminate cleaves the E−NO bond of O-, S-, and N-organonitroso species to give the nickel nitrosyl [Me3NN]NiNO along with dimeric nickel(II) alkoxide or thiolate complexes {[Me3NN]Ni}2(μ-E)2 or the mononuclear nickel(II) amide [Me3NN]NiNPh2. This diamagnetic three-coordinate amide exhibits temperature-dependent NMR spectra due to a low-lying triplet state.