The stabilization of alkoxide anions

1969 ◽  
Vol 47 (12) ◽  
pp. 2306-2307 ◽  
Author(s):  
N. C. Baird
Keyword(s):  
Electron Density ◽  
Molecular Orbital ◽  
Cyclotron Resonance ◽  
Molecular Orbital Calculations ◽  
Ion Cyclotron Resonance ◽  
Density Distributions ◽  
Alkyl Groups ◽  
Valence Electrons ◽  
Ion Cyclotron

Molecular orbital calculations by the MINDO method are reported for the valence electrons of HO− and a number of small alkoxide anions. The acidity order [Formula: see text] is predicted, in agreement with recent ion cyclotron resonance studies. The electron density distributions within the ions are discussed with reference to current models of the polarizability of alkyl groups.

Molecular Mimicry of Structure and Electron Density Distributions in Minerals

1986 ◽  
Vol 73 ◽  
Author(s):  
G. V. Gibbs ◽  
M. B. Boisen
Keyword(s):  
Bond Strength ◽  
Electron Density ◽  
Molecular Orbital ◽  
Computational Models ◽  
Molecular Mimicry ◽  
Strength Parameter ◽  
Molecular Orbital Calculations ◽  
Bond Lengths ◽  
Density Distributions ◽  
Reaction Energies

ABSTRACTMolecular orbital calculations on hydroxyacid molecules with first- and secondrow X-cations (X = Li through N and Na through S) yield bond lengths and angles that mimic those of chemically similar minerals. These bond lengths are used to find a formula giving bond length as a function of a bond-strength parameter that reproduces XO bond lengths in crystals with main-group X-cations from all six rows of the periodic table within 0.05Å on average. The molecular orbital calculations also provide insights into reaction energies, physical properties of crystals such as electron density distributions, and data not amenable to direct measurement. They also provide a basis from which computational models for mineral structures may be constructed.

Gas phase basicity of dihydropyran and dihydro-1,4-dioxin

1986 ◽  
Vol 64 (7) ◽  
pp. 1295-1297 ◽  
Author(s):  
G. Bouchoux ◽  
I. Hanna ◽  
R. Houriet ◽  
E. Rolli
Keyword(s):  
Double Bond ◽  
Proton Transfer ◽  
Gas Phase ◽  
Molecular Orbital ◽  
Cyclotron Resonance ◽  
Transfer Reactions ◽  
Molecular Orbital Calculations ◽  
Ion Cyclotron Resonance ◽  
Lower Reactivity ◽  
Proton Transfer Reactions

The gas phase basicity (GB) of dihydropyran 1 and dihydro-1,4-dioxin 2 is measured in equilibrium proton transfer reactions conducted in an ion cyclotron resonance spectrometer. GB(1) is found to be greater than GB(2) by 37 kJ mol−1, this difference parallels the lower reactivity of 2 observed in solution under acidic condition. Conclusion as to the favoured protonation of the C—C double bond, giving rise for both 1 and 2 to oxycarbonium cations, is drawn from comparison with analogous compounds and substantiated by molecular orbital calculations (MNDO) on the protonated structures.

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