Zirconium complexes supported by an N-perfluoro-arylated diamidopyridyl ligand

• Verfasst von: Scholl, Solveig A. [VerfasserIn]
• Verfasst von: Plundrich, Gudrun [VerfasserIn]
• Verfasst von: Wadepohl, Hubert [VerfasserIn]
• Verfasst von: Gade, Lutz H. [VerfasserIn]
• Titel: Zirconium complexes supported by an N-perfluoro-arylated diamidopyridyl ligand
• Titelzusatz: synthesis of hydrazinediido complexes
• Verf.angabe: Solveig A. Scholl, Gudrun T. Plundrich, Hubert Wadepohl, and Lutz H. Gade
• E-Jahr: 2013
• Jahr: August 13, 2013
• Umfang: 9 S.
• Teil: volume:52
• Teil: year:2013
• Teil: number:17
• Teil: pages:10158-10166
• Teil: extent:9
• Fussnoten: Gesehen am 15.07.2021
• Titel Quelle: Enthalten in: Inorganic chemistry
• Ort Quelle: Washington, DC : American Chemical Society, 1962
• Jahr Quelle: 2013
• Band/Heft Quelle: 52(2013), 17, Seite 10158-10166
• ISSN Quelle: 1520-510X
• DOI: doi:10.1021/ic401603y
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 1762974088

Abstract

The N-perfluoro-phenylated pyridyldiamine H2N2PFPNpy (1) has been prepared by a palladium-catalyzed coupling of hexafluorobenzene and the diamine (H2NCH2)2C(CH3)(2-C5H4N) using the palladacycle trans-di(μ-acetato)bis[o-(di-o-tolylphosphino)benzyl]palladium(II) as catalyst. Reactions of H2N2PFPNpy and Zr(NMe2)4 at room temperature or 90 °C led to the complexes [(NPFPN2TFAPNpy)ZrF(NMe2)] (2) and [(N2TFAPNpy)ZrF2] (3) in which one or two dimethylamido groups replaced one or two ortho fluorine atoms of the pentafluorophenyl groups in the ligand. Reaction of Me3SiX (X = Cl, I) with [(N2TFAPNpy)ZrF2] (3) resulted in the formation of mixed halogenated complexes [(N2TFAPNpy)ZrFI] (4) and [(N2TFAPNpy)ZrFCl] (5) in which the axially bound fluorido ligand is substituted. Reaction of [(N2TFAPNpy)ZrF2] (3) with LiNHNPh2 afforded the monohydrazido(1−) complex [(N2TFAPNpy)ZrF(NHNPh2)] (6) which was converted to the dimeric fluoro-potassium bridged hydrazinediido complex [Zr(N2TFAPNpy)FNNPh2K]2 (7) using KHMDS. The corresponding reaction with LiHMDS yielded the monomeric, donor free complex [Zr(N2TFAPNpy)NNPh2] (8).