Synthesis, Reactivity, and Catalytic Application of a Nickel Pincer Hydride Complex

The nickel­(II) hydride complex [(MeN2N)­Ni-H] (2) was synthesized by the reaction of [(MeN2N)­Ni-OMe] (6) with Ph2SiH2 and was characterized by NMR and IR spectroscopy as well as X-ray crystallography. 2 was unstable in solution, and it decomposed via two reaction pathways. The first pathway was intramolecular N–H reductive elimination to give MeN2NH and nickel particles. The second pathway was intermolecular, with H2, nickel particles, and a five-coordinate Ni­(II) complex [(MeN2N)2Ni] (8) as the products. 2 reacted with acetone and ethylene, forming [(MeN2N)­Ni-OiPr] (9) and [(MeN2N)­Ni-Et] (10), respectively. 2 also reacted with alkyl halides, yielding nickel halide complexes and alkanes. The reduction of alkyl halides was rendered catalytically, using [(MeN2N)­Ni-Cl] (1) as catalyst, NaOiPr or NaOMe as base, and Ph2SiH2 or Me­(EtO)2SiH as the hydride source. The catalysis appears to operate via a radical mechanism.