Zirconium and hafnium (1-pyridinio)imido complexes

• Verfasst von: Herrmann, Heike [VerfasserIn]
• Verfasst von: Gehrmann, Thorsten [VerfasserIn]
• Verfasst von: Wadepohl, Hubert [VerfasserIn]
• Verfasst von: Gade, Lutz H. [VerfasserIn]
• Titel: Zirconium and hafnium (1-pyridinio)imido complexes
• Titelzusatz: functionalized terminal hydrazinediido analogues : dedicated to Professor Brian F.G. Johnson on the occasion of his 70th birthday
• Gefeierte Person: Johnson, Brian F.G. [GefeierteR]
• Verf.angabe: Heike Herrmann, Thorsten Gehrmann, Hubert Wadepohl and Lutz H. Gade
• Jahr: 2008
• Umfang: 11 S.
• Fussnoten: CCDC reference numbers 679492–679494 and 687175–687177. For crystallographic data in CIF or other electronic format see DOI: 10.1039/b807808d ; Gesehen am 13.12.2022
• Titel Quelle: Enthalten in: Dalton transactions
• Ort Quelle: London : Soc., 1972
• Jahr Quelle: 2008
• Band/Heft Quelle: (2008), 44, Seite 6231-6241
• ISSN Quelle: 1477-9234
• DOI: doi:10.1039/B807808D
• Datenträger: Online-Ressource
• Dokumenttyp: Festschrift
• Sprache: eng
• K10plus-PPN: 1826938583

Abstract

Reaction of the diamidozirconium complex [Zr(N2TBSNpy)(NMe2)2] (1) (N2TBSNpy = CH3C(C5H4N)(CH2NSiMe2tBu)2) or the diamidohafnium complex [Hf(N2TBSNpy)(NMe2)2] (2) with one molar equiv. of 1-aminopyridinium triflate in the presence of one equiv. of pyridine gave the corresponding (1-pyridinio)imido complexes [Zr(N2TBSNpy)(N-NC5H5)(OTf)(py)] (3) and [Hf(N2TBSNpy)(N-NC5H5)(OTf)(py)] (4). These were converted to the acetylide complexes [Zr(N2TBSNpy)(N-NC5H5)(CCPh)(py)] (5) and [Hf(N2TBSNpy)(N-NC5H5)(CCPh)(py)] (6) by reaction with lithium phenylacetylide and substitution of the triflato ligand. Upon reaction of 3 and 4 with one molar equivalent of R-NC (R = tBu, Cy, 2,6-xyl), N-N bond cleavage in the (1-pyridinio)imido unit took place and the respective carbodiimido complexes [M(N2TBSNpy](NCNR)(OTf)(py)] (7-12) were formed instantaneously. A similar type of reaction with CO gave the isocyanato complex [Zr(N2TBSNpy](NCO)(OTf)(py)] (13). Finally, the abstraction of the pyridine ligand in compounds 3 and 4 with B(C6F5)3 led to the formation of the triflato-bridged dinuclear complexes [Zr(N2TBSNpy)(N-NC5H5)(OTf)]2 (14) and [Hf(N2TBSNpy)(N-NC5H5)(OTf)]2 (15).