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 (PPOMeP)­Ni­(N2)
(2) and {(PPOMeP)­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.