NC Cleavage in Pincer PNP Complexes of Palladium Academic Article uri icon

abstract

  • Several new N-methylated diarylamine-based PNP pincer ligands have been prepared. The synthesis of these ligands is modular and allows incorporation of a variety of substituants that change the solubility and the stereoelectronic properties of the ligand as well as allow for the introduction of a sensitive 19F NMR spectroscopic probe. The reactions of PN(Me)P ligands with PdX 2 (X = Cl, OAc) initially proceed with formation of an adduct, (PN(Me)P)PdX 2, that may exist in either the neutral or the ionic forms. These adducts are unreactive in the case of PPh 2-bearing ligands, but with the more donating PPr 2i-bearing ligands, the adduct evolves into square planar (PNP)PdX with irreversible loss of MeX. Thus, the feasibility of cleavage of an unstrained N-C bond by Pd II is demonstrated. The N-C cleavage is accelerated by decreasing the solvent polarity. The mechanism may involve either N-C oxidative addition or a nucleophilic attack (external or internal) of X - on the Me group of the N-bound PN(Me)P ligand.

published proceedings

  • Organometallics

altmetric score

  • 6

author list (cited authors)

  • Fan, L., Yang, L., Guo, C., Foxman, B. M., & Ozerov, O. V.

citation count

  • 68

complete list of authors

  • Fan, Lei||Yang, Lin||Guo, Chengyun||Foxman, Bruce M||Ozerov, Oleg V

publication date

  • September 2004