Alternative reaction pathways in domino reactions of hydrazinediidozirconium complexes with alkynes: dedicated to Professor Walter Siebert on the occasion of his 75th birthday
Reaction of [Zr(NAr)2Npy(NMe2)2] (Ar=3,5-xylyl: 2 a, mesityl: 2 b) with one or two molar equivalents of 1,1-diphenylhydrazine gave the mixed amido/hydrazido(1−) complex [Zr(NMes)2Npy(HNNPh2)(NMe2)] (3), the bis-hydrazido complex [Zr(NMes)2Npy(HNNPh2)2] (4), and, in the presence of excess 4-dimethyla...
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| Main Authors: | , , , , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
17 February 2012
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| In: |
Chemistry - a European journal
Year: 2012, Volume: 18, Issue: 13, Pages: 3925-3941 |
| ISSN: | 1521-3765 |
| DOI: | 10.1002/chem.201103497 |
| Online Access: | Verlag, Volltext: http://dx.doi.org/10.1002/chem.201103497 Verlag, Volltext: https://onlinelibrary.wiley.com/doi/abs/10.1002/chem.201103497 
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| Author Notes: | Thorsten Gehrmann, Solveig A. Scholl, Julio Lloret Fillol, Hubert Wadepohl, and Lutz H. Gade |
| Summary: | Reaction of [Zr(NAr)2Npy(NMe2)2] (Ar=3,5-xylyl: 2 a, mesityl: 2 b) with one or two molar equivalents of 1,1-diphenylhydrazine gave the mixed amido/hydrazido(1−) complex [Zr(NMes)2Npy(HNNPh2)(NMe2)] (3), the bis-hydrazido complex [Zr(NMes)2Npy(HNNPh2)2] (4), and, in the presence of excess 4-dimethylaminopyridine (DMAP), hexacoordinate hydrazinediidozirconium complexes [Zr(NXyl)2Npy(NN(Me)Ph)(dmap)2] (5) and [Zr(NXyl)2Npy(NNPh2)(dmap)2] (6). The reaction of one equivalent of the zirconium-hydrazinediide [Zr(NTBS)2Npy(NNPh2)(py)] (1) with disubstituted alkynes at RT for 16 h led to the formation of seven-membered diazazirconacycles 7 a-7 e in high yields. Similar reactivity was observed by reacting bis-amido complex 2 b with one molar equivalent of the corresponding alkyne and diphenylhydrazine. The formation of the seven-membered zirconacycles implied a key coupling step that involved the alkyne and one of the aryl rings of the diphenylhydrazinediido ligand. In some cases, such as the reaction with 2-butyne, the corresponding metallacycle was only obtained in modest yields (45 % for the reaction with 2-butyne) and a second major product, vinylimido complex 9, was formed in almost equal amounts (42 %) by 1,2-amination (formal insertion of the alkyne). The formation of compounds 7 a and 9 followed in part the same sequence of reaction steps and a key intermediate, an azirinido complex, represented a “bifurcation point” in the reaction network. Reaction of 1.2 equivalents of several diarylhydrazines and various substituted alkynes (1 equiv) at ambient temperature (or at 80 °C) in the presence of 10 mol % [Zr(NXyl)2Npy(NMe2)2] (2 a) gave the corresponding indole derivatives. On the other hand, the replacement of 1,1-diarylhydrazines by 1-methyl-1-phenyl hydrazine led to head-to-head cis-1,3-enynes in good yields. |
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| Item Description: | Gesehen am 26.04.2018 |
| Physical Description: | Online Resource |
| ISSN: | 1521-3765 |
| DOI: | 10.1002/chem.201103497 |