Synthesis and Spectroscopic Properties of PdII and PtII 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)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)₂ resulted 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, and ⁷⁷Se NMR) spectroscopy, elemental analysis, and IR spectroscopy. Additionally, the molecular structure of 8 was obtained.