Two-State Reactivity Mechanism of Benzene C-C Activation by Trinuclear Titanium Hydride.
The cleavage of inert C-C bonds is a central challenge in modern chemistry. Multinuclear transition metal complexes would be a desirable alternative because of the synergetic effect of multiple metal centers. In this work, carbon-carbon bond cleavage and rearrangement of benzene by a trinuclear tita...
| Publicado en: | Journal of the American Chemical Society Vol. 138; no. 35; pp. 11069 - 11073 |
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| Autores principales: | , , , |
| Formato: | Artículo |
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American Chemical Society
9/7/2016
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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=118366608&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 118366608 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: 9/7/2016 vid: 138 iid: 35 pid: 997 pub: American Chemical Society artinfo: ui: 118366608 10.1021/jacs.6b02433 ppf: 11069 ppct: 4 formats: tig: atl: Two-State Reactivity Mechanism of Benzene C-C Activation by Trinuclear Titanium Hydride. aug: au: Bo Zhu Wei Guan Li-Kai Yan Zhong-Min Su affil: Institute of Functional Materials Chemistry and Local United Engineering Lab for Power Battery, Faculty of Chemistry, Northeast Normal University, Changchun 130024, P. R. China su: Reaction mechanisms (Chemistry) Carbon-carbon bonds Titanium hydride Activation (Chemistry) Density functional theory sug: subj: Reaction mechanisms (Chemistry) Carbon-carbon bonds Titanium hydride Activation (Chemistry) Density functional theory ab: The cleavage of inert C-C bonds is a central challenge in modern chemistry. Multinuclear transition metal complexes would be a desirable alternative because of the synergetic effect of multiple metal centers. In this work, carbon-carbon bond cleavage and rearrangement of benzene by a trinuclear titanium hydride were investigated using density functional theory. The reaction occurs via a novel "two-state reactivity" mechanism. The important elementary steps consist of hydride transfer, benzene coordination, dehydrogenation, oxidative addition, hydride-proton exchange, and reductive elimination. Most importantly, the ground-state potential energy surface switches from nearly degenerate triplet and antiferromagnetic singlet states to a closed-shell singlet state in the dearomatization of benzene, which effectively decreases the activation barrier. Furthermore, the roles of the transition metal centers and hydrides were clarified. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2016 holdings: @attributes: islocal: N |
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