title: Noninnocent behavior of bidentate amidophosphido [NP]2- ligands upon coordination to copper.
abstract: The synthesis and preliminary coordination chemistry of two new redox-active bidentate ligands containing amido and phosphido donors are described. Treatment of the [(R)NP](2-) (R = Ph, 2,4,6-trimethylphenyl) ligands with CuCl2 and PMe3 results in a dimeric copper(I) P-P coupled product via ligand oxidation. The intermediate of this reaction is proposed to involve a ligand radical generated via oxidation of the [(R)NP](2-) ligand by copper(II), and the existence of such an intermediate is probed using computational methods. Significant radical character on the phosphorus atoms of the alleged [(R)NP](•-)/copper(I) intermediate leads to P-P radical coupling.
authors.affiliation: Department of Chemistry, Brandeis University , 415 South Street, Waltham, Massachusetts 02454, United States.
authors.forename: Mark W
authors.initials: MW
authors.lastname: Bezpalko
authors.forename: Bruce M
authors.initials: BM
authors.lastname: Foxman
authors.forename: Christine M
authors.initials: CM
authors.lastname: Thomas
mesh_terms: D060326:Chemistry Techniques, Synthetic; D003300:Copper / Q000737:chemistry*; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010084:Oxidation-Reduction
chemical_list: D008024:Ligands; D009942:Organometallic Compounds; D003300:Copper