Intrinsic Reactivity of Gaseous Halocarbocations toward Model Aromatic Compounds
| Autor: | Regina Sparrapan, Fabio Cesar Gozzo, Leonardo S. Santos, Marcos N. Eberlin, Ana Elisa Pinto Moreira Sorrilha, Rodinei Augusti |
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| Rok vydání: | 2004 |
| Předmět: | |
| Zdroj: | The Journal of Physical Chemistry A. 108:7009-7020 |
| ISSN: | 1520-5215 1089-5639 |
| Popis: | The gas-phase reactivity of a set of halocarbocations, +CH2X (X = Cl, Br, or I), +CHX1X2 (X1, X2 = F, Cl, or Br), and +CX3 (X = F or Cl), with four prototype aromatic compounds (benzene, furan, pyrrole, and pyridine) was investigated via double- and triple-stage mass spectrometry and compared to that of the simplest +CH3 carbocation. A rich chemistry is observed, and the reaction channels are greatly influenced by the number and type of halogen substituents (X), the strength of the C−X bonds, the nature of the aromatic compound, and the relative stabilities of the carbocation products. [Ar−CH2]+, [Ar−CHX]+, or [Ar−CX1X2]+ functionalization of the relatively inert aromatic Ar−H bonds is the main reaction channel observed. A structure-specific “methylene by hydride exchange” reaction with toluene and B3LYP/6-311G(d,p) calculations indicate that the benzylium ion and the 2-furanylmethyl cation are formed in the [Ar−CH2]+ functionalization of benzene and furan, respectively. Kinetic isotope effects for the [A... |
| Databáze: | OpenAIRE |
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