Effects of polar aprotic solvents on linear free-energy relations in hydrogen-bonded complex formation

1972 ◽  
Vol 94 (10) ◽  
pp. 3438-3442 ◽  
Author(s):  
L. Joris ◽  
J. Mitsky ◽  
R. W. Taft
Keyword(s):  
Free Energy ◽  
Complex Formation ◽  
Aprotic Solvents ◽  
Linear Free Energy ◽  
Energy Relations ◽  
Hydrogen Bonded

The transmission of polar effects. Part VII. A proton magnetic resonance spectra study of substituted mesitylenes, durenes, anthracenes, and triptycenes

1968 ◽  
Vol 46 (24) ◽  
pp. 3903-3908 ◽  
Author(s):  
Keith Bowden ◽  
J. G. Irving ◽  
M. J. Price
Keyword(s):  
Dielectric Constant ◽  
Free Energy ◽  
Carbon Tetrachloride ◽  
Field Effect ◽  
Proton Magnetic Resonance ◽  
Chemical Shifts ◽  
Linear Free Energy ◽  
Solvent Dependence ◽  
Similar Dependence ◽  
Energy Relations

The chemical shifts of the ring protons in a series of monosubstituted mesitylenes and durenes, and of the 10-protons of a series of 9-substituted triptycenes and anthracenes have been measured in dimethyl sulfoxide, acetone, 2-methoxyethanol, and carbon tetrachloride. The solvent dependence of the substituent chemical shifts has been analyzed by linear free energy relations. The systems all show similar dependence which increases with increasing dielectric constant of the solvent. This does not result from the field effect being transmitted through the medium, but appears to arise from the formation of a hydrogen-bonded interaction between the solvent and the hydrogen of the solute. The substituent chemical shifts appear to arise from contributions from substituent field, resonance, magnetic anisotropy, and solvent effects.

Requirements and interpretation of linear free energy relations

1984 ◽  
Vol 106 (10) ◽  
pp. 2772-2774 ◽  
Author(s):  
Peter E. Doan ◽  
Russell S. Drago
Keyword(s):  
Free Energy ◽  
Linear Free Energy ◽  
Energy Relations

Linear free energy relationship rate constants and basicities of N-substituted phenyl glycines in positronium-glycine complex formation

1987 ◽  
Vol 137 (5) ◽  
pp. 471-474 ◽  
Author(s):  
Rongti Chen (Y.T. Chen) ◽  
Jiachang Liang ◽  
Youming Du ◽  
Chun Cao ◽  
Dinzhen Yin ◽  
...  
Keyword(s):  
Free Energy ◽  
Complex Formation ◽  
Rate Constants ◽  
Linear Free Energy Relationship ◽  
Linear Free Energy

Linear free energy relations and the hammett equation for substituted pyridine 1-oxides

1967 ◽  
Vol 4 (4) ◽  
pp. 591-597 ◽  
Author(s):  
John H. Nelson ◽  
Roy G. Garvey ◽  
Ronald O. Ragsdale
Keyword(s):  
Free Energy ◽  
Hammett Equation ◽  
Linear Free Energy ◽  
Energy Relations

The reactions of O(3P) with the butanols

1983 ◽  
Vol 61 (12) ◽  
pp. 2716-2720 ◽  
Author(s):  
John M. Roscoe
Keyword(s):  
Free Energy ◽  
Gas Phase ◽  
Rate Constants ◽  
Substrate Concentration ◽  
Kinetic Data ◽  
Absolute Rate ◽  
Gas Phase Reactions ◽  
Linear Free Energy ◽  
Different Types ◽  
Energy Relations

The reactions of O(3P) with the butanols were studied kinetically as a function of temperature and substrate concentration. The absolute rate constants for the gas phase reactions, in the units M−1 s−1, obey the following relations.[Formula: see text]The results suggest that although the α-CH bond in these alcohols is the most reactive one, reaction of O(3P) with other CH bonds in the alcohols is also appreciable. The kinetic data for these and other alcohols are separated into contributions from the different types of CH bonds and the results are discussed in terms of linear free energy relations.

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