Mononuclear
Pd(I) species are putative intermediates in Pd-catalyzed
reactions, but our knowledge about them is limited due to difficulties
in accessing them. Herein, we report the isolation of a Pd(I) amido
complex, [(BINAP)Pd(NHArTrip)] (BINAP = 2,2′-bis(diphenylphosphino)-1,1′-binaphthalene,
ArTrip = 2,6-bis(2′,4′,6′-triisopropylphenyl)phenyl),
from the reaction of (BINAP)PdCl2 with LiNHArTrip. This Pd(I) amido species has been characterized by X-ray crystallography,
electron paramagnetic resonance, and multiedge Pd X-ray absorption
spectroscopy. Theoretical study revealed that, while the three-electron–two-center
π-interaction between Pd and N in the Pd(I) complex imposes
severe Pauli repulsion in its Pd–N bond, pronounced attractive
interligand dispersion force aids its stabilization. In accord with
its electronic features, reactions of homolytic Pd–N bond cleavage
and deprotonation of primary amines are observed on the Pd(I) amido
complex.
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