The intramolecular hydrogen atom transfer in the photodissociation of o-chlorotoluene
نویسندگان
چکیده
Based on ab initio calculated results, a new mechanism is proposed that intramolecular hydrogen atom transfer may occur Ž . during the photodissociation of o-chlorotoluene at 266 nm. This mechanism is different from the general suggestion, i.e. 1 Ž . Ž . Ž . Ž . o-chlorotoluene S TMo-chlorotoluene T TMClqo-tolylTMbenzylqCl. Our suggestion is 2 o-chlorotoluene S TMo1 1 1 Ž . Ž . Ž . chlorotoluene T , S TM5-methylene-6-chloro-1,3-cyclohexadiene MCC S TMbenzylqCl. Our results show that the 1 0 0 Ž . energy barrier of the rearrangement from o-tolyl to benzyl in path 1 is too high to be overcome, but the intramolecular H Ž . atom transfer of o-chlorotoluene in path 2 may be more reasonable. q 1998 Elsevier Science B.V.
منابع مشابه
Computational study of the intramolecular proton transfer between 6-hydroxypicolinic acid tautomeric forms and intermolecular hydrogen bonding in their dimers
This paper is a density functional theory (DFT) calculation of intramolecular proton transfer (IPT) in 6-hydroxypicolinic acid (6HPA, 6-hydroxypyridine-2-carboxylic acid) tautomeric forms. The transition state for the enol-to-keto transition is reported in the gas phase and in four different solvents. The planar and non-planar dimer forms of 6HPA keto and enol, respectively, were also studied i...
متن کاملThe Influence of Cation-π Interactions on the Strength and Nature of Intramolecular O...H Hydrogen Bond in Orthohydroxy Benzaldehyde Compound
The influence of cation-π interactions on the strength and nature of intramolecular O...H hydrogen bond has been investigated by quantum chemical calculations in orthohydroxy benzaldehyde (HBA) compound. Ab initio calculations have been performed at MP2/6-311++G** level of theory. Vibrational frequencies and physical properties such as chemical potential and chemical hardness of these compounds...
متن کاملDFT-PBE, DFT-D, and MP2 Studies on the H2O•••HNH and HOH•••NH2 Hydrogen Bonds in Water-Aniline Complexes
DFT-GGA method of Perdew-Burke-Ernzerhof (PBE) is used with aug-cc-PVTZ, 6-311++G**, and Def2-TZVP large basis sets to study the hydrogen bond interactions between oxygen lone pair as a donor electron with hydrogen atom connected to the aniline’s nitrogen as an electron acceptor (H2O···HNH-Ph), and nitrogen lone pair with hydrogen of water molecule (Ph-H2N···HOH...
متن کاملHydrogen Adsorption on (5,0) and (3,3) Na-decorated BNNTs
The storage capacity of hydrogen on Na-decorated born nitride nanotubes (BNNTs) is investigated by using density functional theory within Quantum Espresso and Gaussian 09. The results obtained predict that a single Na atom tends to occupy above the central region of the hexagonal rings in (5,0) and (3,3) BNNT structures with a binding energy of -2.67 and -4.28 eV/Na-atom respectively. When a si...
متن کاملRole of Hydrogen Transfer and Ionic Bonding on RR, SS and RS Medetomidine Conglomerates/Acids Stability: A Theoretical Study
This study focuses on RR, SS and RS medetomidine (MM) and inclusion of several achiral acids to distinguish which acid can help conglomerate formation instead of crystallizating racemic mixtures by defining the low-lying energy of their structures. Favorable orientation of acids was determined in interaction with the MM enantiomers after optimization. The most noticeable interactions include hy...
متن کامل