Alkyl Inductive Effects on Molecular Ionization Potentials. XIV. Amides

Widing, H. F.; Levitt, Barbara W.; Levitt, L. S.

doi:10.1002/ijch.197500009

Cited by 4 publications

(1 citation statement)

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“…A number of correlations of ionization potentials of aliphatic compounds with Taft or inductive substituent constants have appeared (9). However, the substituents were restricted to hydrogen or alkyl groups.…”

Section: A Linear Free Energy Relationshipsmentioning

confidence: 99%

Linear free energy relationships. VIII. Ionization potentials of aliphatic compounds

Gibson¹

1977

Can. J. Chem.

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. Can J. Chem. 55,2637Chem. 55, (1977. Ionization potentials (IP) of HX, CH3X, C2H5X, and i-C3H,X, where X is a substituent with non-bonded electrons, are directly proportional to ionization potentials of 4-substituted quinuclidines. This is taken as evidence that in general the energy required to remove an electron from a substituent X, as is the case in HX, CH3X, C,H5X, and i-C3H7X, is directly proportional to the energy required to remove an electron from a site remote from the substituent, as in the quinuclidines in which an electron is lost from the ring nitrogen. Furthermore, the 1P's of the HX-i-C3H7X series are directly proportional to inductive substituent constants, o,, providing a valuable correlation between gas and solution phase behavior.HARRY W. GIBSON. Can. J. Chem. 55,2637(1977. Les potentiels d'ionisation (IP) de HX, CH3X, C2H,X et i-C3H7X, ou X est un substituant comportant des electrons non-lies, sont directement proportionnels aux potentiels d'ionisation des quinuclidines substitues en position 4. On considere cette correlation comme une indication que, d'une facon gtnerale, I'energie requise pour enlever un electron d'un substituant X, comme dans le cas de HX, CH3X, C2H5X et i-C3H7X, est directement proportionnelle a l'energie requise pour enlever un electron d'un site eloigne du substituant comme dans les quinuclidines dans lesquelles un electron est perdu par I'azote du cycle. De plus, les potentiels d'ionisation de la serie HX CC3H7X sont directenient proportionnels aux constantes inductives des substituants, o,, fournissant une correlation tres utile entre le comportemellt en phase gazeuse et en solution.[Traduit par le journal] Molecular orbital energy levels are determining factors both for chemical reactivity and many physical properties, especially spectral and electrical properties. Our previous work using linear free energy relationships (1-7), including the Hammett equation (8), was aimed at quantitatively relating these energy levels to molecular structure (1-4,6,7) and in turn to electrical properties (5) of aromatic compounds. In the first paper of this series it was shown that the ionization potentials (IP) of substituted benzenes are linearly related to the sums of the Hammett substituent constants. To understand and predict the properties of aliphatic series a similar linear free energy relationship would be most helpful. A . Linear Free Energy RelationshipsA number of correlations of ionization potentials of aliphatic compounds with Taft or inductive substituent constants have appeared (9). However, the substituents were restricted to hydrogen or alkyl groups. The only exception is the study of some quinuclidines (1) (lo), in which sitbstituents with non-bonded electrons were examined. It was our objective to deter-'References 1-7 comprise parts I-VII of this series. mine if the ionization potentials of simple alkanes substituted with groups bearing nonbonded electrons could be correlated with the ionization potentials of series 1 and more generally with substituent const...

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Section: A Linear Free Energy Relationshipsmentioning

confidence: 99%