Phosphinite-Ni(0) Mediated Formation of a Phosphide-Ni(II)-OCOOMe Species via Uncommon Metal–Ligand Cooperation

Reversible transformations are observed between a phosphide-nickel­(II) alkoxide and a phosphinite-nickel(0) species via a P–O bond formation coupled with a 2-e^– redox change at the nickel center. In the forward reaction, the nickel(0) dinitrogen species (PP^OMeP)­Ni­(N₂) (<b>2</b>) and {(PP^OMeP)­Ni}₂(μ-N₂) (<b>3</b>) were formed from the reaction of (PPP)­NiCl (<b>1</b>) with a methoxy anion. In the backward reaction, a (PPP)­Ni­(II) moiety was regenerated from the CO₂ reaction of <b>3</b> with the concomitant formation of a methyl carbonate ligand in (PPP)­Ni­(OCOOMe) (<b>7</b>). Thus, unanticipated metal–ligand cooperation involving a phosphide based ligand is reported