Reductive eliminations
to form alkyl–nitrogen bonds are
rare, and examples of this reaction from isolated complexes containing
simple, unstabilized primary alkyl groups have not been observed.
We report the synthesis of stable neopentylpalladium(II) anilido and
methyleneamido complexes that undergo reductive elimination to form
the C(sp3)–N bonds in N-neopentyl
anilines and N-neopentyl imines, respectively. The
synthesis and isolation of these complexes were enabled by weak chelation
of palladium by P,O ancillary ligands. DFT calculations suggest that
neopentylpalladium(II) complexes undergo reductive elimination by
a concerted mechanism resembling a migration of the alkyl ligand to
the nitrogen either following initial dissociation of the oxygen donor
or in concert with lengthening of the Pd–O bond, depending
on the identities of the reacting and ancillary ligands.