Zirconium complexes supported by an N-perfluoro-arylated diamidopyridyl ligand: synthesis of hydrazinediido complexes

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 an...

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Bibliographic Details
Main Authors: Scholl, Solveig A. (Author) , Plundrich, Gudrun (Author) , Wadepohl, Hubert (Author) , Gade, Lutz H. (Author)
Format: Article (Journal)
Language:English
Published: August 13, 2013
In: Inorganic chemistry
Year: 2013, Volume: 52, Issue: 17, Pages: 10158-10166
ISSN:1520-510X
DOI:10.1021/ic401603y
Online Access:Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1021/ic401603y
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Author Notes:Solveig A. Scholl, Gudrun T. Plundrich, Hubert Wadepohl, and Lutz H. Gade
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Summary: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).
Item Description:Gesehen am 15.07.2021
Physical Description:Online Resource
ISSN:1520-510X
DOI:10.1021/ic401603y