New mono- and bis(pentafluorophenyl)palladium(II) complexes with iminophosphine ligands. Crystal structure of [Pd(C_6F_5)(SC_6H_5)(o-Ph_2PC_6H_4-CH=N~iPr)]

摘要

The synthesis of new mono- and bis(pentafluorophenyl)derivatives of palladium(II) with the mixed-dohor bidentate ligands o-Ph_2PC_6H_4-CH=NR (RN-P)has been achieved. The new complexes of general formula [Pd(C6Fs)_2(RN-P)] [R = Me (I), Et (2). "Pr (3) iPr (4), 'Bu(5), Ph (6), NH-Me (7)rand [Pd (C_6F_5)Cl(RN-P)][R =Me (8), 'Pr (9), NH-Me (10)] have been, respectively, prepared by reaction between the labile precursors cis-[Pd(C_6F_5h(PhCN)_2] or [{Pd(C_6F_5)(tht)(J.l-CI)r1] (tht= tetrahydrothiophene) and the corresponding iminophosphines. Complex (9) undergoes metathetical exchange of chloride with anionic monodentateligands when reacting with alkaline salts, giving the complexes of formula [Pd(C_6F_5)XtPrN -P)] [X = Br (II), I (12), CN (13), SCN (14), SC6H5 (15). p-SC6H4Me (16), p-SC_6H_4NO" (17), OMe (18)]. Furthermore, when the chloropentafluorophenyl complex (9) was treated with silver trifluoromethanesulfonate in the presence of tertiary phosphines, the cationic derivatives [Pd(C_6F_5)(L)tPrN-P)](CF_3SO_3)[L = PEt3(19), PMe_2Ph (20), PMePh_2 (21)] were obtained in good yield. The new complexes were characterized by partial elemental. analyses and spectroscopic methods (IR, lH, '9F and 3fPNMR). The molecular structure of complex (15) has been determined bya single-crystal diffraction study, showing that the iminophosphine act as chelating ligand with coordination around the palladium atom slight distorted from the square-planargeometry.