Synthesis and Spectroscopic Properties of Pd^IIand Pt^IIComplexes 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)Ph₂)(PPh₂) [E = S (2), Se (3)], respectively. Reactions of 2 and 3 with MCl₂(cod) (M = Pd, Pt) afforded [MCl₂{2-κ²P,S}] [M = Pd(4), Pt(5)] and [MCl₂{3-κ²P,Se}] [M = Pd(6), Pt(7)], respectively. In contrast, reactions of the same ligands with NiCl₂(PPh₃)₂resulted in deselenization and desulfurization, producing complex 8 with the formula [NiCl₂{1-κ²P,P}]. Ligands 2 and 3, as well as their complexes 4–7 and 8 were identified and characterized by multinuclear NMR (¹H,¹³C,³¹P, and⁷⁷Se NMR) spectroscopy, elemental analysis, and IR spectroscopy. Additionally, the molecular structure of 8 was obtained.