Reactivity of a cationic square-planar palladium(II) chloro complex containing bis[2-(diphenylphosphino)ethyl]amine: chloro substitutions by anionic ligands and formation of neutral digold(I) compounds possessing linear PAuX fragments. The X-Ray crys

摘要

The interaction of sodium tetrachloropalladate(II) with the potentially tridentate aminophosphine bis[2-(diphenylphosphino)ethyl]amine (PNHP) in 1:1 molar rato lead to the formation of the four-coordinate complex [Pd(PNHP)Cl]Cl (1). Complex 1 undergoes chloro substitution reactions with NaX (X = Br, I), CuCl, AgNO_3, the amino acid N-acetyl-L-cysteine (AcCysSH) and the tripeptide reduced glutathione (#gamma#-L-Glu-L-Cys-Gly, GSH) affording [Pd(PNHP)X]X' [X = X' = Br (2), I(3), NO_3 (4); X = Cl, X' = CuCl_2 (1a); X' = Cl, X = RS = AcCysS (8), GS(9)]. However, gold(I) induces abstration of the aminophosphine from the ionic complexes 1 and 2 to produce the neutral compounds Au_2(PNHP)X_2 [X = Cl (5), Br(6)]. The dinuclear complex Au_2(PN(NO)P)Cl_2 (5a), containing the ligand bis[2-(diphenylphosphino)ethyl]nitrosylamine, was formed by reaction of 4 with gold(I) in the presence of traces of nitrosyl chloride. Addition of one molar equivalent of PNHP to 1 results, by a ring-opening process, in the formation of [Pd(PNHP)_2]Cl_2 (7) in which the palladium is five-coordinate. The ionic complexes 1,2 and 4 were shown by X-ray diffraction to be distorted square-planar and complex 2 has a N-H…Br bond of 2.371 A with the ligand adopting a boat conformation. The X-ray crystal structure of the novel neutral compound 5a shows linear P-Au-Cl arrangements with intermolecular Au…Au interactions of 3.0412(9) A.