Thermal stability of O-H and O-alkyl bonds in N-alkoxyamines.: A density functional theory approach
Thermal stability of O-H and O-alkyl bonds in N-alkoxyamines.: A density functional theory approach
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DOI：
10.1021/jp990202l
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发表时间：
1999-04-15
影响因子：
2.9
通讯作者：
Claire, PD
中科院分区：
文献类型：
--
作者：
Marsal, P;Roche, M;Claire, PD
烷氧胺中O-C键离解能(δ H（r)度(T)）在氮氧基介导的活性自由基聚合过程中起关键作用，δ H(r)度(T)在20 ~ 30 kcal/mol之间可实现有效控制。本文用密度泛函理论计算了不同羟胺和烷氧胺的O-H和O-C键离解能。优化程序，基础设置的影响，和交换相关功能进行比较，并对实验数据进行了测试。最后，报道了（n -叔丁基-1-二乙基膦-2,2-二甲基丙基氮氧化物）的键解离能R "（其中R " =苄基，苯乙烯）。最后的结果尤其重要，因为SG1是迄今为止在苯乙烯和丙烯酸酯的氮氧化物介导聚合中最有效的氮氧化物自由基。
The O-C bond dissociation energy (Delta H(r)degrees(T)) in alkoxyamines appears to play a key role in the nitroxide-mediated living free radical polymerizations, and an efficient control of the process can be achieved for Delta H(r)degrees(T) between 20 and 30 kcal/mol. We report in this paper density functional theory calculations of the O-H and O-C bond dissociation energies of different hydroxylamines and alkoxyamines. Optimization procedures, basis set effects, and exchange-correlation functionals are compared and tested against experimental data. Finally, the bond dissociation energy of (N-tert-butyl-1-diethylphosphono-2,2-dimethylpropylnitroxide)R " (where R " = benzyl, styryl), is reported. This last result is especially important since SG1 is the most efficient to-date nitroxide radical in nitroxide-mediated polymerizations of styrene and acrylates.