M. García-Seijo, A. Habtemariam, S. Parsons
2002
Citations
0
Influential Citations
21
Citations
Journal
New Journal of Chemistry
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 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.