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 C 10 H 7 ‐1‐N(P( E )Ph 2 )(PPh 2 ) [ E = S ( 2 ), Se ( 3 )], respectively. Reactions of 2 and 3 with M Cl 2 (cod) ( M = Pd, Pt) afforded [ M Cl 2 { 2 ‐κ 2 P,S }] [ M = Pd( 4 ), Pt( 5 )] and [ M Cl 2 { 3 ‐κ 2 P,Se }] [ M = Pd( 6 ), Pt( 7 )], respectively. In contrast, reactions of the same ligands with NiCl 2 (PPh 3 ) 2 resulted in deselenization and desulfurization, producing complex 8 with the formula [NiCl 2 {1‐κ 2 P,P }]. Ligands 2 and 3 , as well as their complexes 4 – 7 and 8 were identified and characterized by multinuclear NMR ( 1 H, 13 C, 31 P, and 77 Se NMR) spectroscopy, elemental analysis, and IR spectroscopy. Additionally, the molecular structure of 8 was obtained.