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Radical Stability—A Theoretical Perspective

  • H. ZipseEmail author
Chapter
Part of the Topics in Current Chemistry book series (TOPCURRCHEM, volume 263)

Abstract

The thermodynamic stability of radicals as defined through isodesmic hydrogen transfer reactions has been explored at a variety of theoretical levels. Radical stabilization energies (RSEs) derived from single point calculations at the ROMP2/6-311+G(3df,2p)//UBecke3LYP/6-31G(d) level of theory in combination with scaled zero point vibrational energies calculated at the UBecke3LYP/6-31G(d) level have been determined for a broad variety of systems. For the three radical types considered in this study (carbon-, nitrogen-, and oxygen-centered radicals) the radical stabilization energy (RSE) depends on the same fundamental effects such as resonance stabilization of the unpaired spin, electron donation through adjacent alkyl groups or lone pairs, and through inductive electron donation/electron withdrawal. The influence of ring strain effects as well as the synergistic combination of individual substituent effects have also been explored.

DFT calculations Isodesmic equations Radicals ROMP2 calculations Thermodynamic stability 

Abbreviations

BDE

bond dissociation energy

CBS

complete basis set theory

DFT

density functional theory

G3

Gaussian-3 theory

HLC

higher level correction terms

ROMP2

2nd order restricted open shell Møller–Plesset theory

RSE

radical stabilization energy

W1

Weizmann-1 theory

W2

Weizmann-2 theory

ZPVE

zero point vibrational energy

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Authors and Affiliations

  1. 1.Department of Chemistry and BiochemistryLMU MünchenMünchenGermany

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