Properties of atoms in molecules: dipole moments and substituent effects in ethyl and carbonyl compounds

1988 ◽  
Vol 92 (22) ◽  
pp. 6219-6227 ◽  
Author(s):  
Tom Slee ◽  
Annie Larouche ◽  
Richard F. W. Bader
Keyword(s):  
Carbonyl Compounds ◽  
Dipole Moments ◽  
Substituent Effects ◽  
Atoms In Molecules

Substituent effects on basicity in Group 15 compounds: an analysis based on proton affinities, charge distributions, and dipole polarizabilities

1997 ◽  
Vol 75 (1) ◽  
pp. 60-67 ◽  
Author(s):  
S.T. Howard ◽  
J.P. Foreman ◽  
P.G. Edwards
Keyword(s):  
Electric Field ◽  
Charge Distribution ◽  
Proton Affinity ◽  
Dipole Moments ◽  
Substituent Effects ◽  
Atoms In Molecules ◽  
Proton Affinities ◽  
Electric Field Gradients ◽  
Field Gradients ◽  
Dipole Polarizabilities

Ab initio calculations on a series of trisubstituted amines, phosphines, and arsines are presented at the MP2/6-311G(d,p) level. Specifically, the species studied are XH3, XF3, and X(Me)3, where X = N, P, or As. The influence of the substituents on the proton affinity is analyzed in terms of the charge distribution, its topology, some one-electron properties (dipole moments, electric field gradients), and dipole polarizabilities. An atoms-in-molecules. decomposition of the charge distribution, energetics, and polarizabilities also proves informative. There seems to be no straightforward way of rationalizing the basicities of these compounds on the basis of electrostatic properties (i.e., properties of the charge distribution in the unprotonated bases). However, substituent effects on basicities can be correlated with response properties, such as the molecular (and atoms-in-molecules) polarizability tensors, and the amount of charge that a substituent group or atom donates on protonation. Key words: quantum chemistry, proton affinity, electron density, lone pairs, polarizability, basicity, dipole moment, electric field gradient.

An Analysis of Substituent Effects in Ethane Derivatives: The Quantum Theory of Atoms in Molecules Approach

2009 ◽  
Vol 113 (6) ◽  
pp. 1105-1110 ◽  
Author(s):  
Slawomir J. Grabowski ◽  
Tadeusz M. Krygowski ◽  
Jerzy Leszczynski
Keyword(s):  
Quantum Theory ◽  
Substituent Effects ◽  
Atoms In Molecules

Properties of atoms in molecules: Dipole moments and transferability of properties

1987 ◽  
Vol 87 (2) ◽  
pp. 1142-1152 ◽  
Author(s):  
R. F. W. Bader ◽  
A. Larouche ◽  
C. Gatti ◽  
M. T. Carroll ◽  
P. J. MacDougall ◽  
...  
Keyword(s):  
Dipole Moments ◽  
Atoms In Molecules

scholarly journals Carbonyl Addition Reactions: Factors Affecting the Hydrate–Hemiacetal and Hemiacetal–Acetal Equilibrium Constants

1975 ◽  
Vol 53 (6) ◽  
pp. 898-906 ◽  
Author(s):  
J. Peter Guthrie
Keyword(s):  
Aqueous Solution ◽  
Carbonyl Compounds ◽  
Equilibrium Constants ◽  
Substituent Effects ◽  
Steric Effects ◽  
Addition Reactions ◽  
Free Energies ◽  
Electronic Effects ◽  
Factors Affecting ◽  
Analogous Formula

Equilibrium constants for hydrate–hemiacetal interconversion in aqueous solution at 25° have been measured for four fluorinated carbonyl compounds: compound, alcohol, K4 (M−1): CF3CHO, C2H5OH, 2.3; CF3COCH3, CH3OH, 1.0; CF3COPh, CH3OH, 3.5; CF3COCF3, CH3OH, 0.14. These values, combined with values from the literature, permit an examination of substituent effects upon the equilibrium constant for[Formula: see text]The free energy change for this process, corrected for symmetry and steric effects, follows the equation[Formula: see text]Thus electronic effects upon this equilibrium are generally small and in fact are often smaller than steric effects.This analysis permits and justifies the calculation of free energies of formation of [Formula: see text] compounds from the (more generally measurable) free energies of formation of the analogous [Formula: see text] compounds.

scholarly journals Studies of Hydrogen Bonding. Part XXXIV. Dipole Moments of Carbonyl Compounds and of their Hydrogen-Bonded Complexes with Phenol.

1993 ◽  
Vol 47 ◽  
pp. 68-71 ◽  
Author(s):  
Thor Gramstad ◽  
Stephen L. Buchwald ◽  
John F. Richardson ◽  
Anders Hallberg ◽  
Jörgen Alvhäll ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Carbonyl Compounds ◽  
Dipole Moments ◽  
Bonded Complexes ◽  
Hydrogen Bonded
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