BRIDGING IN BETA-CHLOROALKYL RADICALS BY ELECTRON-SPIN RESONANCE
BRIDGING IN BETA-CHLOROALKYL RADICALS BY ELECTRON-SPIN RESONANCE
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DOI：
10.1021/ja00797a039
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发表时间：
1973-01-01
影响因子：
15
通讯作者：
KOCHI, JK
中科院分区：
文献类型：
--
作者：
CHEN, KS;ELSON, IH;KOCHI, JK
Ca-Cf) 键和 Cg 处的畸变，使重叠的氯原子更靠近自由基中心的 p 轨道。各向同性 ESR g 值和温度依赖性氯 35 和质子超精细分裂的分析表明，所有这些/3-氯烷基自由基都以由不对称桥中的氯组成的稳定构象存在。甲基促进桥接，但抵消空间效应会阻止四甲基类似物实现对称桥接结构。据报道，β-氯异丁基中的氯可以轻松地 1, 2 迁移至叔异构体。
Ca-Cf) bond and distortion at Cg which places the eclipsed chlorine atomcloser to the p orbital at the radical center. Analysis of isotropic esr g values and temperature-dependent chlorine-35 and proton hyperfine splittings in-dicates that all these/3-chloroalkyl radicals exist in stable conformations consisting of chlorine in asymmetric bridges. Bridging is promoted by methyl groups, but counteracting steric effects prevent the tetramethyl analog from achieving a symmetric bridged structure. The facile 1, 2 migration of chlorine in the ß-chloroisobutyl radical to the tertiary isomer is reported.