Gas-phase proton-transfer and substitution reactions: energy dependence and dissociation dynamics

1993 ◽  
Vol 115 (23) ◽  
pp. 10823-10829 ◽  
Author(s):  
James L. Wilbur ◽  
Brian D. Wladkowski ◽  
John I. Brauman
Keyword(s):  
Proton Transfer ◽  
Gas Phase ◽  
Energy Dependence ◽  
Substitution Reactions ◽  
Dissociation Dynamics

An experimental study of the reactivity of the hydroxide anion in the gas phase at room temperature, and its perturbation by hydration

1981 ◽  
Vol 59 (11) ◽  
pp. 1615-1621 ◽  
Author(s):  
Scott D. Tanner ◽  
Gervase I. Mackay ◽  
Diethard K. Bohme
Keyword(s):  
Experimental Study ◽  
Proton Transfer ◽  
Gas Phase ◽  
Rate Constants ◽  
Room Temperature ◽  
Gas Phase Reactions ◽  
Flowing Afterglow ◽  
Hydroxide Anion

Flowing afterglow measurements are reported which provide rate constants and product identifications at 298 ± 2 K for the gas-phase reactions of OH− with CH3OH, C2H5OH, CH3OCH3, CH2O, CH3CHO, CH3COCH3, CH2CO, HCOOH, HCOOCH3, CH2=C=CH2, CH3—C≡CH, and C6H5CH3. The main channels observed were proton transfer and solvation of the OH−. Hydration with one molecule of H2O was observed either to reduce the rate slightly and lead to products which are the hydrated analogues of the "nude" reaction, or to stop the reaction completely, k ≤ 10−12 cm3 molecule−1 s−1. The reaction of OH−•H2O with CH3—C≡CH showed an uncertain intermediate behaviour.

Gas-phase proton-transfer reactions of the hydronium ion at 298 K

1979 ◽  
Vol 57 (12) ◽  
pp. 1518-1523 ◽  
Author(s):  
Gervase I. Mackay ◽  
Scott D. Tanner ◽  
Alan C. Hopkinson ◽  
Diethard K. Bohme
Keyword(s):  
Proton Transfer ◽  
Gas Phase ◽  
Rate Constants ◽  
Transfer Reactions ◽  
Flowing Afterglow ◽  
Hydronium Ion ◽  
Proton Transfer Reactions

Rate constants measured with the flowing afterglow technique at 298 ± 2 K are reported for the proton-transfer reactions of H3O+ with CH2O, CH3CHO, (CH3)2CO, HCOOH, CH3COOH, HCOOCH3, CH3OH, C2H5OH, (CH3)2O, and CH2CO. Dissociative proton-transfer was observed only with CH3COOH. The rate constants are compared with the predictions of various theories for ion–molecule collisions. The protonation is discussed in terms of the energetics and mechanisms of various modes of dissociation.

scholarly journals Reactions between neutral molecules and cation-radicals in the gas-phase: Can protonation occur without proton transfer?

2015 ◽  
Vol 390 ◽  
pp. 39-48
Author(s):  
Yury V. Vasil’ev ◽  
Douglas F. Barofsky ◽  
Joseph S. Beckman ◽  
Benjamin J. Bythell
Keyword(s):  
Proton Transfer ◽  
Gas Phase ◽  
Cation Radicals

Collision-induced elimination of alkenes from deprotonated unsaturated ethers in the gas phase. Reactions involving specific .beta.-proton transfer

1990 ◽  
Vol 112 (7) ◽  
pp. 2537-2541 ◽  
Author(s):  
Russell J. Waugh ◽  
Roger N. Hayes ◽  
Peter C. H. Eichinger ◽  
K. M. Downard ◽  
John H. Bowie
Keyword(s):  
Proton Transfer ◽  
Gas Phase ◽  
Gas Phase Reactions

STUDIES ON NUCLEOPHILIC SUBSTITUTION REACTIONS AT CARBON (SN2(C)) AND SILICON (SN2(Si)) IN TERMS OF AB INITIO, POTENTIAL, ACTING ON AN ELECTRON IN A MOLECULE AND MOLECULAR FACE THEORY

2009 ◽  
Vol 08 (supp01) ◽  
pp. 983-1001 ◽  
Author(s):  
YAN-LI DING ◽  
LI-DONG GONG ◽  
DONG-XIA ZHAO ◽  
MING-BO ZHANG ◽  
ZHONG-ZHI YANG
Keyword(s):  
Ab Initio ◽  
Nucleophilic Substitution ◽  
Gas Phase ◽  
Chemical Bond ◽  
Energy Transition ◽  
High Energy ◽  
Ab Initio Method ◽  
Substitution Reactions ◽  
Nucleophilic Substitution Reactions ◽  
High Energy Transition

The gas-phase identity bimolecular nucleophilic substitution reactions, Cl- + CH3 Cl → ClCH3 + Cl- and Cl- + SiH3Cl → ClSiH3 + Cl- , are investigated in terms of the ab initio method, potential acting on an electron in a molecule (PAEM) and molecular face (MF) theory. The computations have been performed at the CCSD(T)/aug-cc-pVTZ//MP2/6-311+G(3df,3pd) and CISD/aug-cc-pVDZ level. Based on the ab initio calculation, according to the PAEM theory, the strength of a chemical bond during forming or rupturing may be characterized by the D pb , which is a new physical quantity relating to the barrier height of the PAEM along a chemical bond. According to the MF theory, the interesting pictures of electron transfer and interpolarization effect between the reactants are clearly demonstrated to provide visualized spatial changing features of the MF for the title reactions along the IRC routes. The reason why [ Cl⋯CH3⋯Cl]- is a high-energy transition state is also analyzed in comparison with the stable low-energy intermediate [ Cl⋯SiH3⋯Cl]- .

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