| Zugriffsnummer | 40239 |
| Dokumenttyp | Zeitschriftenartikel |
| Peer Review | mit Peer Review |
| Sprache | Englisch |
| Titel | Doubly and triply charged species formed from chlorobenzene reveal unusual C-Cl multiple bonding |
| Autor(in); Institution |
Fantuzzi, Felipe; Universidade Federal do Rio de Janeiro, Instituto de Química, Rio de Janeiro, BRAZIL
Rudek, Benedikt; 6.5, Strahlenwirkung, PTB-Braunschweig
Wolff, Wania; Universidade Federal do Rio de Janeiro, Instituto de Física, Rio de Janeiro, BRAZIL
Chaer Nascimento, Marco Antonio; Universidade Federal do Rio de Janeiro, Instituto de Química, Rio de Janeiro, BRAZIL
|
| Quelle/Jahr | Journal of the American Chemical Society: 140 (2018), 12, 4288 - 4292 |
| ISSN | 0002-7863 (PRINT) ; 1520-5126 (ONLINE) |
| DOI | |
| Verlag | Washington, D.C.: ACS Publications |
| Freie Schlagworte | Fragmentation ; density functional theory ; hydrocarbons |
| Zusammenfassung | 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 (C6H5Cl) 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, rC−Cl = 1.621 Å) and a ketene-like C=C=Cl cumulated species (2, rC−Cl = 1.542 Å). The calculations suggest that an excited state of 2 has a nitrile-like C=Cl triple bond structure. |
