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- W2057804975 abstract "Addition of trimethylsilyl (Me3Si·) and methylthiyl (MeS·) radical to Me3SiCH2–CHCH2 and MeSCH2–CHCH2 yields, respectively, the radicals Me3SiCH2ĊHCH2SiMe3(I) and MeSCH2ĊHCH2SMe (II) which were observed by e.s.r. spectroscopy. Restricted rotation about the ·CH–CH2 bonds was detected below –100 °C and the free energy of activation determined [3.4 for (I) and 2.85 kcal mol–1 for (II), respectively]. The features of the line shapes also showed that the conformation of (I) is symmetric whereas that of (II) is asymmetric. The geometry of these conformations was also assessed and the angle ϕ between the 2pz orbital of ·CH and the C–X bond was found to be 4–5°§ when X = SiMe3(I) and 10–11° when X = MeS (II). The dependence of the β-splitting on the conformation and on the electronic properties of silicon and sulphur was studied by INDO calculations and the hypothesis that sulphur-containing radicals must be distorted to account for their low aHβ splitting is challenged." @default.
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- W2057804975 date "1982-01-01" @default.
- W2057804975 modified "2023-10-18" @default.
- W2057804975 title "Stereodynamical processes in β-substituted symmetric isopropyl radicals" @default.
- W2057804975 doi "https://doi.org/10.1039/p29820000043" @default.
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