ChemRxiv | 2021
An Isolable Mononuclear Palladium(I) Amido Complex
Abstract
Mononuclear Pd(I) species are putative intermediates in Pd-catalyzed reactions, but our\nknowledge about them is limited due to difficulties in accessing them. Herein, we report the\nisolation of a Pd(I) amido complex, [(BINAP)Pd(NHArTrip )] (BINAP = 2,2′-\nbis(diphenylphosphino)-1,1′-binaphthalene, ArTrip = 2,6-bis(2’,4’,6’-triisopropylphenyl)phenyl),\nfrom the reaction of (BINAP)PdCl2 with LiNHArTrip. This Pd(I) amido species has been\ncharacterized 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\nbond, pronounced attractive inter-ligand dispersion force aids its stabilization. In accord with its\nelectronic features, reactions of homolytic Pd–N bond cleavage and deprotonation of primary\namines are observed on the Pd(I) amido complex.