The synthesis and preliminary coordination chemistry of two new redox-active bidentate ligands containing amido and phosphido donors are described. Treatment of the [(NP)-N-R](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 [(NP)-N-R](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 [(NP)-N-R](center dot-)/copper(I) intermediate leads to P-P radical coupling.