Competition between electron transfer and base-induced elimination mechanisms in the gas-phase reactions of superoxide with alkyl hydroperoxides

2021 ◽  
Vol 23 (9) ◽  
pp. 5583-5595
Author(s):  
Ezequiel Fragoso Vieira Leitão ◽  
Miguel Angelo Fonseca de Souza ◽  
Silmar Andrade do Monte ◽  
Elizete Ventura
Keyword(s):  
Electron Transfer ◽  
Gas Phase ◽  
Superoxide Anion ◽  
Methyl Ethyl ◽  
Gas Phase Reactions ◽  
Alkyl Hydroperoxides

Elucidating the possible pathways in the mechanisms of the superoxide anion reactions with methyl, ethyl and tert-butyl hydroperoxides.

Gas-phase heteroaromatic substitution. 11. Electron transfer mechanism in the gas-phase acylation of simple five-membered heteroarenes

1991 ◽  
Vol 69 (4) ◽  
pp. 740-748 ◽  
Author(s):  
Antonello Filippi ◽  
Giorgio Occhiucci ◽  
Cinzia Sparapani ◽  
Maurizio Speranza
Keyword(s):  
Electron Transfer ◽  
Gas Phase ◽  
Reaction Products ◽  
Ion Chemistry ◽  
Gas Phase Reactions ◽  
Β Decay ◽  
Electron Transfer Mechanism ◽  
Gas Phase Ion Chemistry ◽  
Mass Spectrometric Evidence ◽  
Gas Phase Ion

The results of a study of the gas-phase reactions of unsaturated carbocations, such as the CH3CO+ ion from γ-radiolysis of CH3F/CO mixtures, and the C6H4TCO+ ion from the β-decay of 1,4-ditritiobenzene in the presence of CO, with pyrrole, N-methylpyrrole, furan, and thiophene, are reported. In all systems investigated, acylated heteroarenes represent the predominant reaction products, accompanied by the methylated derivatives in the CH3F/CO radiolytic mixtures, and by the phenylated ones in the 1,4-ditritiobenzene/CO decay samples. All substrates investigated are found to undergo predominant α substitution by both acetyl (88.6–98.4% (pyrrole); 90.8–98.7% (N-methylpyrrole); 97.2–98.9% (furan); 94.9–98.6% (thiophene)) and benzoyl cations (92.6–96.5% (pyrrole)) under all conditions. The predominant formation of the α-acylated pyrroles from both reactants (>88%), whose relative yields appear unaffected within the temperature interval from 303 to 383 K, indicates, in agreement with ancillary FT-ICR mass spectrometric evidence, that gas-phase acylation reactions toward simple five-membered heteroarenes proceed via a two-step substitution mechanism, involving a quasi-resonant single-electron transfer (SET) step followed by recombination of the ensuing radical – radical ion pair. By virtue of this entropy-favored mechanism, gaseous electrophiles with relatively high SCF STO-3G calculated LUMO energies such as CH3CO+ and C6H4TCO+ are effectively oriented toward the "soft" Cα sites of the selected heteroarenes, at variance with Klopman's Charge and Frontier Orbital Control predictions. The behavior of gaseous acylating reactants toward simple heteroarenes is discussed and compared with that of other gaseous electrophiles, whose reactivity appears instead in qualitative agreement with Klopman's model. Key words: gas-phase ion chemistry, electrophilic heteroaromatic substitution, nuclear decay and radiolysis, acylium ions, electron transfer.

Gas-Phase Reactions

1981 ◽  
Author(s):  
Victor N. Kondratiev ◽  
Evgeniĭ E. Nikitin
Keyword(s):  
Gas Phase ◽  
Gas Phase Reactions

Influence of Gas Mixing and Heating on Gas-Phase Reactions in GaN MOCVD Growth

2012 ◽  
Vol 1 (1) ◽  
pp. P46-P53 ◽  
Author(s):  
Ran Zuo ◽  
Haiqun Yu ◽  
Nan Xu ◽  
Xiaokun He
Keyword(s):  
Gas Phase ◽  
Gas Mixing ◽  
Gas Phase Reactions ◽  
Mocvd Growth

Gas Phase Reactions Activated by Nuclear Processes

1957 ◽  
Vol 79 (17) ◽  
pp. 4609-4616 ◽  
Author(s):  
Adon A. Gordus ◽  
John E. Willard
Keyword(s):  
Gas Phase ◽  
Gas Phase Reactions ◽  
Nuclear Processes
Sign in / Sign up

Export Citation Format

Share Document