Synthesis and Spectroscopic Properties of Pd-II and Pt-II Complexes with Monosulfide and Monoselenide Bis(phosphanyl)amine Ligands

Oxidation of N,N-bis(diphenylphosphanyl)naphthalen-1-amine (1) with elemental sulfur or gray selenium (1:1 molar ratio) gave the corresponding monosulfide and monoselenide bis(phosphanyl)amine ligands C10H7-1-N(P(E)Ph-2)(PPh2) [E = S (2), Se (3)], respectively. Reactions of 2 and 3 with MCl2(cod) (M = Pd, Pt) afforded [MCl2{2-kappa P-2, S}] [M = Pd(4), Pt(5)] and [MCl2{3-kappa P-2,Se}] [M = Pd(6), Pt(7)], respectively. In contrast, reactions of the same ligands with NiCl2(PPh3)(2) resulted in deselenization and desulfurization, producing complex 8 with the formula [NiCl2{1-kappa P-2,P}]. Ligands 2 and 3, as well as their complexes 4-7 and 8 were identified and characterized by multinuclear NMR (H-1, C-13, P-31, and Se-77 NMR) spectroscopy, elemental analysis, and IR spectroscopy. Additionally, the molecular structure of 8 was obtained.