Comparison of gas-phase acidities of some carbon acids with their rates of hydron exchange in methanolic methoxide

2006 ◽  
Vol 19 (5) ◽  
pp. 308-317 ◽  
Author(s):  
Vincent F. DeTuri ◽  
Heinz F. Koch ◽  
Judith G. Koch ◽  
Gerrit Lodder ◽  
Masaaki Mishima ◽  
...  
Keyword(s):  
Gas Phase ◽  
Carbon Acids

Marcus theory and the existence or non-existence of transition states in gas phase deprotonation of carbon acids

1984 ◽  
Vol 62 (8) ◽  
pp. 1465-1469 ◽  
Author(s):  
Saul Wolfe
Keyword(s):  
Proton Transfer ◽  
Gas Phase ◽  
Transition States ◽  
Marcus Theory ◽  
Energy Change ◽  
Transfer Reactions ◽  
Gas Phase Reactions ◽  
Proton Transfer Reactions ◽  
Carbon Acids ◽  
Computational Level

At the 3-21G (3-21G*) computational level, the intrinsic barriers associated with proton transfer between XCH2− and CH3X have been found to be essentially constant (ca. 10 kcal/mol) for X = H, F, SH, Cl. According to the Marcus rate-equilibrium treatment of proton transfer reactions, this result means that transition states should not exist for gas phase reactions [Formula: see text], when the energy change exceeds 20 kcal/mol. This prediction has been confirmed for two cases (X = H, F) in which the energy change is less than 20 kcal/mol, and two cases (X = SH, Cl) in which the energy change is greater than 20 kcal/mol.

scholarly journals A theoretical study of the limits of the acidity of carbon acids in phase transfer catalysis in water and in liquid ammonia

2013 ◽  
Vol 11 (11) ◽  
pp. 1711-1722 ◽  
Author(s):  
Ibon Alkorta ◽  
José Elguero ◽  
Roger Gallo
Keyword(s):  
Experimental Data ◽  
Gas Phase ◽  
Liquid Ammonia ◽  
Phase Transfer Catalysis ◽  
Theoretical Study ◽  
Phase Transfer ◽  
Dmso Solution ◽  
Homogeneous Set ◽  
Carbon Acids

AbstractThe acidities of a large number of carbon acids have been theoretically calculated for the gas-phase and for DMSO solution. The gas-phase values, both ΔH and ΔG, are very well correlated with the available experimental data. From the calculated ΔG values in DMSO and the pKas in the same solvent, a homogeneous set of pK a (DMSO) values was devised that was used to generate pK a (water). These last pK as were used to establish the limits of the acidity of carbon acids for reactions under PTC conditions both alkylations and H/D exchange. A step further led to the pK as in liquid ammonia and from them to the virtual use of PTC using liquid ammonia instead of water.

Acidities of carbon acids. V. Correlation of acidities in dimethyl sulfoxide with gas-phase acidities

1975 ◽  
Vol 97 (11) ◽  
pp. 3226-3227 ◽  
Author(s):  
F. G. Bordwell ◽  
John E. Bartmess ◽  
George E. Drucker ◽  
Zafra Margolin ◽  
Walter S. Matthews
Keyword(s):  
Dimethyl Sulfoxide ◽  
Gas Phase ◽  
Carbon Acids

ChemInform Abstract: ACIDITIES OF CARBON ACIDS PART 5, CORRELATION OF ACIDITIES IN DIMETHYL SULFOXIDE WITH GAS-PHASE ACIDITIES

1975 ◽  
Vol 6 (33) ◽  
Author(s):  
F. G. BORDWELL ◽  
JOHN E. BARTMESS ◽  
GEORGE E. DRUCKER ◽  
ZAFRA MARGOLIN ◽  
WALTER S. MATTHEWS
Keyword(s):  
Dimethyl Sulfoxide ◽  
Gas Phase ◽  
Carbon Acids

Alkyl effects on equilibrium acidities of carbon acids in protic and dipolar aprotic media and the gas phase

1978 ◽  
Vol 43 (16) ◽  
pp. 3095-3101 ◽  
Author(s):  
F. G. Bordwell ◽  
John E. Bartmess ◽  
Judith A. Hautala
Keyword(s):  
Gas Phase ◽  
Carbon Acids
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