Doubly and Triply Charged Species Formed from Chlorobenzene Reveal Unusual C-Cl Multiple Bonding.
In free-radical halogenation of aromatics, singly charged ions are usually formed as intermediates. These stable species can be easily observed by time-of-flight mass spectrometry (TOF-MS). Here we used electron and proton beams to ionize chlorobenzene (CHCl) and investigate the ions stability by TO...
| Publicado en: | Journal of the American Chemical Society Vol. 140; no. 12; pp. 4288 - 4293 |
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| Autores principales: | , , , |
| Formato: | Artículo |
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American Chemical Society
3/28/2018
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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=128802224&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 128802224 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: 3/28/2018 vid: 140 iid: 12 pid: 997 pub: American Chemical Society artinfo: ui: 128802224 10.1021/jacs.7b12749 ppf: 4288 ppct: 5 formats: tig: atl: Doubly and Triply Charged Species Formed from Chlorobenzene Reveal Unusual C-Cl Multiple Bonding. aug: au: Fantuzzi, Felipe Rudek, Benedikt Wolff, Wania Nascimento, Marco Antonio Chaer affil: Instituto de Química, Universidade Federal do Rio de Janeiro, Rio de Janeiro, RJ 21941-909, Brazil Physikalisch-Technische Bundesanstalt, Bundesallee 100, 38116 Braunschweig, Germany Instituto de Física, Universidade Federal do Rio de Janeiro, Rio de Janeiro, RJ 21941-972, Brazil su: Halogenation Chlorobenzene Density functional theory Rare earth metals Actinide elements sug: subj: Halogenation Chlorobenzene Density functional theory Rare earth metals Actinide elements ab: In free-radical halogenation of aromatics, singly charged ions are usually formed as intermediates. These stable species can be easily observed by time-of-flight mass spectrometry (TOF-MS). Here we used electron and proton beams to ionize chlorobenzene (CHCl) and investigate the ions stability by TOF-MS. Additionally to the singly charged parent ion and its fragments, we find a significant yield of doubly and triply charged parent ions not previously reported. In order to characterize these species, we used high-level theoretical methods based on density functional theory (DFT), coupled-cluster (CC), and generalized valence bond (GVB) to calculate the structure, relative stabilities, and bonding of these dications and trications. The most stable isomers exhibit unusual carbon-chlorine multiple bonding: a terminal C==Cl double bond in a formyl-like CHCl moiety (1, r = 1.621 Å) and a ketene-like C==C==Cl cumulated species (2, r = 1.542 Å). The calculations suggest that an excited state of 2 has a nitrile-like C==Cl triple bond structure. 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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