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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| Main Authors: | , , , |
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| Format: | Article (Journal) Festschrift |
| Language: | English |
| Published: |
2008
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| In: |
Dalton transactions
Year: 2008, Issue: 44, Pages: 6231-6241 |
| ISSN: | 1477-9234 |
| DOI: | 10.1039/B807808D |
| Subjects: | |
| 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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| 245 | 1 | 0 | |a Zirconium and hafnium (1-pyridinio)imido complexes |b functionalized terminal hydrazinediido analogues : dedicated to Professor Brian F.G. Johnson on the occasion of his 70th birthday |c Heike Herrmann, Thorsten Gehrmann, Hubert Wadepohl and Lutz H. Gade |
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| 520 | |a 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). | ||
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