Reaction of Cp*(CI)M(Diene) (M = Ti, Hf) with Isonitriles.
We have investigated the reaction of isonitriles (RNC) with electronically unsaturated diene complexes of Ti and Hf. Cp*(Cl)Ti(2,3-dimethylbutadiene) (1) reacts with 2 equiv of RNC to give η,η-diimine complexes 2 (R = Bu) and 3 (R = 1-adamantyl). Cp*(Cl)Ti(N,N-di-Bu-η,η-diimine) (2), in the presence...
| Publicado en: | Journal of the American Chemical Society Vol. 137; no. 32; pp. 10152 - 10156 |
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| Autores principales: | , , |
| Formato: | Artículo |
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American Chemical Society
8/19/2015
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| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=109259488&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 109259488 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 8/19/2015 vid: 137 iid: 32 pid: 997 pub: American Chemical Society artinfo: ui: 109259488 10.1021/jacs.5b06654 ppf: 10152 ppct: 4 formats: tig: atl: Reaction of Cp*(CI)M(Diene) (M = Ti, Hf) with Isonitriles. aug: au: Valadez, Travis N. Norton, Jack R. Neary, Michelle C. affil: Department of Chemistry, Columbia University, New York, New York 10027, United States su: Isocyanides Diolefins Pyridine Hafnium Cyclopropanation sug: subj: Isocyanides Diolefins Pyridine Hafnium Cyclopropanation ab: We have investigated the reaction of isonitriles (RNC) with electronically unsaturated diene complexes of Ti and Hf. Cp*(Cl)Ti(2,3-dimethylbutadiene) (1) reacts with 2 equiv of RNC to give η,η-diimine complexes 2 (R = Bu) and 3 (R = 1-adamantyl). Cp*(Cl)Ti(N,N-di-Bu-η,η-diimine) (2), in the presence of pyridine, fragments to Cp*(Cl)Ti(NBu)(NCH) (10) and an α-methylene cyclopent-3-enimine (11). The hafnium analogue of 1, Cp*(Cl)Hf(2,3-dimethylbutadiene) (14), has been reported to give a cyclic amidine complex when treated with 2 equiv of 2,6-dimethylphenyl isonitrile. By X-ray crystallography, however, we find that 14 and 2,6-dimethylphenyl isonitrile give instead a 2,5-diazahafnacyclopentane that features a σ-interaction between the C-C bond of a cyclopropane ring and the Hf. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2015 holdings: @attributes: islocal: N |
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