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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 carboncarbon 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 ( = ˙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, C6H4pCN, C6H4pNO2, C6H4pOCH3, C6H4pOH, CF2CF3, CF2H, CF3, CCl2H, CCl3, CH2Cl, CH2F, CH2OH, CH2Ph, cyclo-CH(CH2)2, CH2CH[double bond, length as m-dash]CH2, CH2CH3, CH(CH3)2, C(CH3)3, C[triple bond, length as m-dash]CH, CH[double bond, length as m-dash]CH2, CH[double bond, length as m-dash]CHCH3, 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.

Graphical abstract: A comparison of methods for measuring relative radical stabilities of carbon-centred radicals

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