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 multi-edge Pd Xray absorption spectroscopy. Theoretical study revealed that, while the 3-electron-2-center π interaction between Pd and N in the Pd(I) complex imposes severe Pauli repulsion in its Pd–N
bond, pronounced attractive inter-ligand 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.
Theoretical Study of the Ti–Cl Bond Cleavage Reaction in TiCl4
