819870-25-2Relevant academic research and scientific papers
Palladium(II) amido complexes with an unsymmetrical PNP′ pincer-type coordination and a new (E,E)-tetradentate diphosphinoazine coordination mode
Storch, Jan,?ermák, Jan,Vojtií?ek, Pavel,Císa?ová, Ivana
, p. 4165 - 4171 (2004)
Cationic palladium(II) complexes [PdCl{PR2CH 2C(But)NNC(But)CH2PR2}] Cl (R=Pri, c-C6H11, But) were synthesized. Their reactions with triethylamine gave complexes [PdCl{PR 2CHC(But)NNC(But)CH2PR 2}], containing deprotonated diphosphinoazines in ene-hydrazone unsymmetrical pincer-like configuration which represent several of the still rare examples of Pd(II) amido bis(phosphine) complexes. A novel (E,E) tetradentate coordination mode of diphosphinoazines was also discovered. Cationic palladium(II) complexes [PdCl{PR2CH2C(Bu t)NNC(But)CH2PR2}]Cl, where R = isopropyl, cyclohexyl or tert-butyl, were synthesized by the reactions of the corresponding diphosphinoazines with bis(acetonitrile)palladium(II) dichloride. When bis(benzonitrile)palladium(II) dichloride was used instead, in the molar ratio of 2:1 to the diphosphinoazine, a new complex was isolated with the isopropyl ligand showing a previously unknown (E,E) tetradentate coordination mode. Crystal and molecular structure was determined by X-ray diffraction. The solid complex was a racemate of two axially chiral enantiomers and the chirality was preserved in solution. Reactions of the cationic complexes with triethylamine gave complexes [PdCl{PR2CHC(But)NNC(Bu t)CH2PR2}], containing deprotonated diphosphinoazines in ene-hydrazone unsymmetrical pincer-like configuration. The complexes represent several of the still rare examples of Pd(II) amido bis(phosphine) complexes with a chlorine atom covalently bonded trans to the amide nitrogen.
