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Master equations for calculating heterolysis energies in solution

Journal Article · · Energy Fuel; (United States)
DOI:https://doi.org/10.1021/ef00001a003· OSTI ID:6572428

A simple master equation for predicting the heterolysis energies of bonds to give resonance-stabilized ions is tested by reaction of six carbocations with 21 carbanions and four phenoxide anions. The original equation is enormously improved in precision and generality by replacing pK/sub R+/ values as the measure of cation stability. If calculated ..pi.. delocalization energies are used, data for 33 reactions are correlated by eq 5 with r = 0.9948 (instead of r = 0.8812) so that the standard deviation of ..delta..H/sub het/ is +/- 0.702 kcal/mol. With ..delta..H/sub het/ for 9-(methoxycarbonyl)fluorenide anion as the model anion, 66 values are correlated with r = 0.9960, proving the self-consistency of their data as well as the soundness of this approach. Equations such as (5) should provide a simple means for estimating quantitative heterolysis energies in solution for thousands of bonds that give resonance-stabilized ions as products. 23 references, 6 figures, 1 table.

Research Organization:
Duke Univ., Durham, NC
OSTI ID:
6572428
Journal Information:
Energy Fuel; (United States), Journal Name: Energy Fuel; (United States) Vol. 1:1; ISSN ENFUE
Country of Publication:
United States
Language:
English