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(OMe)P)Ni(N2) (2) and {(PP(OMe)P)Ni}2(μ-N2) (3) were formed from the reaction of (PPP)NiCl (1) with a methoxy anion. In the backward reaction, a (PPP)Ni(II) moiety was regenerated from the CO2 reaction of 3 with the concomitant formation of a methyl carbonate ligand in (PPP)Ni(OCOOMe) (7). Thus, unanticipated metal-ligand cooperation involving a phosphide based ligand is reported.