On the Advantages of Hydrocarbon Radical Stabilization Energies Based on R-H Bond Dissociation Energies

被引：22

作者：

Wodrich, Matthew D. ^{[3
]}

McKee, W. Chad ^{[1
,2
]}

Schleyer, Paul von Rague ^{[1
,2
]}

机构：

[1] Univ Georgia, Dept Chem, Athens, GA 30602 USA

[2] Univ Georgia, Ctr Computat Chem, Athens, GA 30602 USA

[3] Univ Geneva, Sch Chem & Biochem, CH-1211 Geneva 4, Switzerland

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2011年 / 76卷 / 08期

关键词：

PARADIGM SHIFTING IMPLICATIONS; STAGGERED CONFORMATION; THEORETICAL-ANALYSIS; INTERNAL-ROTATION; STERIC ANALYSIS; DIPOLE-MOMENT; ALKYL-GROUPS; I-PR; ENTHALPIES; ELECTRONEGATIVITY;

D O I：

10.1021/jo101661c

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Hydrocarbon radical stabilization energy (RSE) estimates based on the differences in R-H vs CH3-H bond dissociation energies have inherent advantages over RSEs based on R-CH3 vs CH3-CH3, as well as R-R vs CH3-CH3 comparisons, since the R-CH3 and R-R reference systems are prone to unbalanced contaminating intramolecular interactions involving the R groups. When the effects of steric crowding, branching, protobranching conjugation, and hyperconjugation are taken into account, R-CH3 and R-R based RSE values are nearly identical to R-H RSEs. Corrections for electronegativity differences between H and R are not needed to achieve agreement.

引用

页码：2439 / 2447

页数：9

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