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 crystal structure of Au2[Ph2P(CH2)2N(NO)(CH2)2PPh2]Cl2

New Journal of Chemistry Pub Date: 2002-05-23 DOI: 10.1039/B109675N

Abstract

The interaction of sodium tetrachloropalladate(II) with the potentially tridentate aminophosphine bis[2-(diphenylphosphino)ethyl]amine (PNHP) in 1∶1 molar ratio leads 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, AgNO3, the amino acid N-acetyl-L-cysteine (AcCysSH) and the tripeptide reduced glutathione (γ-L-Glu-L-Cys-Gly, GSH) affording [Pd(PNHP)X]X′ [X?=?X′?=?Br (2), I (3), NO3 (4); X?=?Cl, X′?=?CuCl2 (1a); X′?=?Cl, X?=?RS?=?AcCysS (8), GS (9)]. However, gold(I) induces abstraction of the aminophosphine from the ionic complexes 1 and 2 to produce the neutral compounds Au2(PNHP)X2 [X?=?Cl (5), Br (6)]. The dinuclear complex Au2(PN(NO)P)Cl2 (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]Cl2 (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 ? 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) ?.

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