A comparison of methods for measuring relative radical stabilities of carbon-centred radicals‡

Literature Information

Publication Date 2010-06-16
DOI 10.1039/C003880F
Impact Factor 3.676
Authors

Michelle L. Coote, Ching Yeh Lin, Athelstan L. J. Beckwith, Andreas A. Zavitsas


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Abstract

This article discusses and compares various methods for defining and measuring radical stability, including the familiar radical stabilization energy (RSE), along with some lesser-known alternatives based on corrected carbon–carbon bond energies, and more direct measures of the extent of radical delocalisation. As part of this work, a large set of R–H, R–CH3, R–Cl and R–R BDEs (R˙ = ˙CH2X, ˙CH(CH3)X, ˙C(CH3)2X and X = H, BH2, CH3, NH2, OH, F, SiH3, PH2, SH, Cl, Br, N(CH3)2, NHCH3, NHCHO, NHCOCH3, NO2, OCF3, OCH2CH3, OCH3, OCHO, OCOCH3, Si(CH3)3, P(CH3)2, SC(CH3)2CN, SCH2COOCH3, SCH2COOCH3, SCH2Ph, SCH3, SO2CH3, S(O)CH3, Ph, C6H4–pCN, C6H4–pNO2, C6H4–pOCH3, C6H4–pOH, CF2CF3, CF2H, CF3, CCl2H, CCl3, CH2Cl, CH2F, CH2OH, CH2Ph, cyclo-CH(CH2)2, CH2CHCH2, CH2CH3, CH(CH3)2, C(CH3)3, CCH, CHCH2, CHCHCH3, CHO, CN, COCH3, CON(CH2CH3)2, CONH2, CONHCH3, COOC(CH3)3, COOCH2CH3, COOCH3, COOH, COPh), and associated radical stability values are calculated using the high-level ab initio molecular orbital theory method G3(MP2)-RAD. These are used to compare the alternative radical stability schemes and illustrate principal structure–reactivity trends.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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