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Zirconium and hafnium (1-pyridinio)imido complexes: functionalized terminal hydrazinediido analogues : dedicated to Professor Brian F.G. Johnson on the occasion of his 70th birthday

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 c...

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Bibliographic Details
Main Authors: Herrmann, Heike (Author) , Gehrmann, Thorsten (Author) , Wadepohl, Hubert (Author) , Gade, Lutz H. (Author)
Format: Article (Journal) Festschrift
Language:English
Published: 2008
In: Dalton transactions
Year: 2008, Issue: 44, Pages: 6231-6241
ISSN:1477-9234
DOI:10.1039/B807808D
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Festschrift
Online Access:Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1039/B807808D
Verlag, lizenzpflichtig, Volltext: https://pubs.rsc.org/en/content/articlelanding/2008/dt/b807808d
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Author Notes:Heike Herrmann, Thorsten Gehrmann, Hubert Wadepohl and Lutz H. Gade
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Summary: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).
Item Description:CCDC reference numbers 679492–679494 and 687175–687177. For crystallographic data in CIF or other electronic format see DOI: 10.1039/b807808d
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Physical Description:Online Resource
ISSN:1477-9234
DOI:10.1039/B807808D

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