Unimolecular Reaction Pathways of a γ‑Ketohydroperoxide from Combined Application of Automated Reaction Discovery Methods.
Ketohydroperoxides are important in liquid-phase autoxidation and in gas-phase partial oxidation and pre-ignition chemistry, but because of their low concentration, instability, and various analytical chemistry limitations, it has been challenging to experimentally determine their reactivity, and on...
| Publicado en: | Journal of the American Chemical Society Vol. 140; no. 3; pp. 1035 - 1049 |
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| Autores principales: | , , , , , |
| Formato: | Artículo |
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American Chemical Society
1/24/2018
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| Materias: | |
| 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=127646886&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 127646886 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: 1/24/2018 vid: 140 iid: 3 pid: 997 pub: American Chemical Society artinfo: ui: 127646886 10.1021/jacs.7b11009 ppf: 1035 ppct: 14 formats: tig: atl: Unimolecular Reaction Pathways of a γ‑Ketohydroperoxide from Combined Application of Automated Reaction Discovery Methods. aug: au: Grambow, Colin A. Jamal, Adeel Yi-Pei Li Green, William H. Zádor, Judit Suleimanov, Yury V. affil: Department of Chemical Engineering, Massachusetts Institute of Technology, 77 Massachusetts Ave., Cambridge, Massachusetts 02139, United States Combustion Research Facility, Sandia National Laboratories, 7011 East Ave., Livermore, California 94551, United States Computation-based Science and Technology Research Center, Cyprus Institute, 20 Kavafi Str., Nicosia 2121, Cyprus su: Intermediates (Chemistry) Organic synthesis Oxidation Unimolecular reactions Density functional theory Transition state theory (Chemistry) Hydroperoxides sug: subj: Intermediates (Chemistry) Organic synthesis Oxidation Unimolecular reactions Density functional theory Transition state theory (Chemistry) Hydroperoxides ab: Ketohydroperoxides are important in liquid-phase autoxidation and in gas-phase partial oxidation and pre-ignition chemistry, but because of their low concentration, instability, and various analytical chemistry limitations, it has been challenging to experimentally determine their reactivity, and only a few pathways are known. In the present work, 75 elementary-step unimolecular reactions of the simplest γ-ketohydroperoxide, 3-hydroperoxypropanal, were discovered by a combination of density functional theory with several automated transition-state search algorithms: the Berny algorithm coupled with the freezing string method, single- and double-ended growing string methods, the heuristic KinBot algorithm, and the single-component artificial force induced reaction method (SC-AFIR). The present joint approach significantly outperforms previous manual and automated transition-state searches - 68 of the reactions of γ-ketohydroperoxide discovered here were previously unknown and completely unexpected. All of the methods found the lowest-energy transition state, which corresponds to the first step of the Korcek mechanism, but each algorithm except for SC-AFIR detected several reactions not found by any of the other methods. We show that the low-barrier chemical reactions involve promising new chemistry that may be relevant in atmospheric and combustion systems. Our study highlights the complexity of chemical space exploration and the advantage of combined application of several approaches. Overall, the present work demonstrates both the power and the weaknesses of existing fully automated approaches for reaction discovery which suggest possible directions for further method development and assessment in order to enable reliable discovery of all important reactions of any specified reactant(s). pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2018 holdings: @attributes: islocal: N |
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