Organophosphorus ligands with XPNSO skeleton (X = O, S) and their Pd(II) complexes. Crystal and molecular structure of [{XP(OEt)2}(O2SR)]NH (X = O, R = Me, Ph; X = S, R = C6H4Cl-4) and Pd[{SP(OEt)2}(O2SC6H4Cl-4)N

Abstract

Several organophosphorus acids of type [{XP(OEt)2}(O2SR)]NH [X=O, R=Me (1), Ph (2), C6H4CH3-4 (3); X=S, R=C6H4Cl-4 (4)] were obtained by a method based on the reaction between (EtO)2P(X)NHLi and the corresponding organosulfonyl chloride. They were subsequently deprotonated with KOBut. Salt metathesis reactions between PdCl2 and the corresponding potassium salts K[{XP(OEt)2}(O2SR)N] [X=O, R=Me (5), Ph (6), C6H4CH3-4 (7); X=S, R=C6H4Cl-4 (8)] in a 1:2 molar ratio resulted in palladium(II) complexes of type Pd[{XP(OEt)2}(O2SR)N]2 [X=O, R=Me (9), Ph (10), C6H4CH3-4 (11); X=S, R=C6H4Cl-4 (12)]. In a similar way was obtained the palladium(II) complex Pd[(SPPh2)(O2SPh)N]2 (13), using the appropriate reagents. All compounds were characterized by multinuclear NMR (1H, 13C, 31P) and infrared spectroscopy. The potassium salts and the palladium complexes were investigated also by mass spectrometry. Single-crystal X-ray diffraction studies revealed a layered supramolecular assembly in case of acid 1, a monomeric structure for compound 4, while in case of compound 2 dimeric associations are formed in the solid state by NH⋯OP hydrogen bonding. A trans-S,N-coordination pattern of the organophosphorus ligand was found in the palladium complex 12. Moreover, short Cl⋯H contacts result in a polymeric [Pd[{SP(OEt)2}(O2SC6H4Cl-4)N]2]n chain.