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Publication Details
AFRICAN RESEARCH NEXUS
SHINING A SPOTLIGHT ON AFRICAN RESEARCH
chemistry
Computational investigations on base-catalyzed diaryl ether formation
Journal of Organic Chemistry, Volume 78, No. 11, Year 2013
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Description
We report investigations with the dispersion-corrected B3LYP density functional method on mechanisms and energetics for reactions of group I metal phenoxides with halobenzenes as models for polyether formation. Calculated barriers for ether formation from para-substituted fluorobenzenes are well correlated with the electron-donating or -withdrawing properties of the substituent at the para position. These trends have also been explained with the distortion/interaction energy theory model which show that the major component of the activation energy is the energy required to distort the arylfluoride reactant into the geometry that it adopts at the transition state. Resonance-stabilized aryl anion intermediates (Meisenheimer complexes) are predicted to be energetically disfavored in reactions involving fluorobenzenes with a single electron-withdrawing group at the para position of the arene, but are formed when the fluorobenzenes are very electron-deficient, or when chelating substituents at the ortho position of the aryl ring are capable of binding with the metal cation, or both. Our results suggest that the presence of the metal cation does not increase the rate of reaction, but plays an important role in these reactions by binding the fluoride or nitrite leaving group and facilitating displacement. We have found that the barrier to reaction decreases as the size of the metal cation increases among a series of group I metal phenoxides due to the fact that the phenoxide becomes less distorted in the transition state as the size of the metal increases. © 2013 American Chemical Society.
Authors & Co-Authors
Jones, Gavin O.
United States, San Jose
Ibm Research - Almaden
Al Somaa, Ali
Saudi Arabia, Riyadh
King Abdulaziz City for Science and Technology
O'Brien, Jeannette M.
United States, San Jose
Ibm Research - Almaden
Albishi, Hassan
Saudi Arabia, Riyadh
King Abdulaziz City for Science and Technology
Al-Megren, Hamid A.
Saudi Arabia, Riyadh
King Abdulaziz City for Science and Technology
Alabdulrahman, Abdullah M.S.
Saudi Arabia, Riyadh
King Abdulaziz City for Science and Technology
Alsewailem, Fares D.
Saudi Arabia, Riyadh
King Abdulaziz City for Science and Technology
Hedrick, James L.
United States, San Jose
Ibm Research - Almaden
Rice, Julia E.
United States, San Jose
Ibm Research - Almaden
Horn, Hans W.
United States, San Jose
Ibm Research - Almaden
Statistics
Citations: 16
Authors: 10
Affiliations: 2
Identifiers
Doi:
10.1021/jo400550c
ISSN:
00223263
e-ISSN:
15206904