Mechanistic Investigation of the Generation of a Palladium(0) Catalyst from a Palladium(II) Allyl Complex: A Combined Experimental and DFT Study

Cross-coupling reactions can be efficiently catalyzed using palladium complexes. The formation of low-coordinated, highly reactive Pd(0), which is believed to be the catalytic species, is critical. The mechanism of the reduction of a stable and readily available allyl Pd(II) complex into Pd(0) by a combination of K2CO3 and PhB(OH)(2) has been studied. We report on the characterization of the associated reactive solution using a combination of density functional theory and experimental methods. First, the stoichiometric reaction of an (allyl)(phosphine)palladium(II) complex with K2CO3 was first investigated using trandem mass spectrometry. A palladium-carbonate complex could be characterized in the electrospray mass spectrum of the reactive solution. Gas-phase infrared spectra of mass-selected complexes have been recorded, giving further information on the coordination mode (kappa(1)) of the carbonate ligand. This structural information derived from spectroscopy is critical because the relative energy of the two kappa(1) and kappa(2)-carbonate isomers is difficult to determine theoretically, presumably because of the charge transfers at play between the carbonate and the palladium. Second, the product of the stoichiometric addition of PhB(OH)(2) to this carbonate complex was investigated. Both P-31 and H-1 NMR data provide compelling evidence for the formation of the desired 14-electron Pd(0) complex.