452281-80-0Relevant articles and documents
Synthesis, characterization, and reactivity of cationic palladium(II) and platinum(II) iodo complexes containing a linear or a tripodal aminophosphine the. X-ray crystal structures of [Pd{HN(CH2CH2PPh2)2}I]I and [Pd3{N(CH2CH2PPh2}3) 2I4]I2
Ins Garca-Seijo,Habtemariam, Abraha,Fernndez-Anca, Damin,Parsons, Simon,Esther Garca-Fernndez
, p. 1075 - 1084 (2002)
The complexes [M(PNHP)I]I (PNHP = bis[2-(diphenylphosphino)ethyl]amine; M = Pd (1), Pt (2)) and [M(NP3)I]I (NP3 = tris[2-(diphenylphosphino)ethyl]amine; M = Pd (3), Pt (4)) were prepared by interaction of the appropriate aminophosphine in CH2Cl2 with aqueous solutions containing [MCl4]2- salts and NaI in a ratio 1:4. Complexes 2 and 3 form the polynuclear compounds [Pt2(PNHP)3]I4 (2a) and [Pd3(NP3)2I4]I2 (3a) in the presence of coordinating solvents such as the mixture CD3OD/D2O/DMSO-d6 and CH2Cl2/CH3OH, respectively. Complex 1 consists of distorted square-planar cations [Pd(PNHP)I]+ and iodide anions able to establish short N-H···I interactions of 2.850 A. The aminophosphine adopts a boat conformation and is coordinated to palladium in a tridentate chelating fashion. The crystal structure for cations of 3a reveals the presence of two types of distorted square-planar PdII atoms, PdNP2I and trans-PdP2I2, NP3 acting as tridentate chelating and bridging ligand, respectively. On the basis of 31P {1H} NMR data it has been shown that each distorted square-planar Pt(II) centre of 2a contains one PNHP acting as tridentate chelating ligand with the other aminophosphine bridging the two metals via the P atoms. Complexes 3 and 4 were shown by 31P {1H} NMR to have the metal atom bound to the three P atoms of NP3 and one iodo ligand. Additions of AcCysSH and GSH to 4 result, by a ring-opening process, in the formation of [Pt(NP2PO)(SR)] (RS = Acys (4a), GS (4b)) in which the ligand contains a dangling arm phosphine oxide group and the platinum atom achieves the four-coordination involving the N atom of the aminophosphine. Compounds [Pt2(PNHP)3]Cl4 (2a′, 2a″), [PtAu(PNHP)2I]I2 (2b), and [Pt(PNHP)(ONO2)](NO3) (2c) were detected in some extent in solution by reaction of complex 2 with Au(tdg)Cl (tdg = thiodiglycol), AuI and excess AgNO3, respectively. While 1 does not react with AuI, complex 3 affords the heterobimetallic complexes PdCu(NP3)I3 (5), PdAg2(NP3)I4 (6) and PdAu(NP3)I3 (7) by interaction with the appropriate iodide M′I (M′ = Cu, Ag, Au) via a chelate ring-opening.
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
Garcia-Seijo, M. Ines,Habtemariam, Abraha,Parsons, Simon,Gould,Garcia-Fernandez, M. Esther
, p. 636 - 644 (2007/10/03)
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.
