Three-Coordinate β-Diketiminato Nickel Nitrosyl Complexes from Nickel(I)−Lutidine and Nickel(II)−Alkyl Precursors

The nickel(I) β-diketiminates [Me 2 NN]Ni(2,4-lutidine) and [2,4,6-Me 3 NN]Ni(2,4-lutidine) react with NO to form diamagnetic, three-coordinate Ni−NO complexes, and [Me 2 NN]Ni(NO) undergoes insertion with a nitrosobenzene to form the N -aryl- N -nitrosohydroxylaminato species [Me 2 NN]Ni(η 2 -O 2 N 2 Ar). Addition of 2 equiv of NO to the Ni(II)−monoalkyl species [Me 2 NN]Ni(Et)(2,4-lutidine) at room temperature provides an alternate route to [Me 2 NN]Ni(NO), while NO addition at −78 °C favors the formation of [Me 2 NN]Ni(η 2 -O 2 N 2 Et).