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第2课-特殊速率定律、键离解能和相对反应性

Lecture 2 - Peculiar Rate Laws, Bond Dissociation Energies, and Relative Reactivities
课程网址: http://videolectures.net/yalespan125bs2011_mcbride_lec02/  
主讲教师: J. Michael McBride
开课单位: 耶鲁大学
开课时间: 2014-08-19
课程语种: 英语
中文简介:
奇怪的动力学顺序可以提供机械方面的信息。分数动力学阶数表明,占主导地位的聚集体离解,产生较小的反应性物种。由于与二级过程的竞争,一个明显的负动力学级导致手性晶体的自发去乙酰化。键离解能的变化可能是由于键或自由基的不同。尽管人们常说烷基自由基稳定性的顺序是叔级>仲级>一级,但仔细的分析表明,键离解能的顺序可能是由于烷烃而不是自由基中的差异。哈蒙德建议更多放热反应的过渡态在结构和能量上应更接近起始材料,从而帮助有机化学家开始系统地思考预测相对反应速率。
课程简介: Curious kinetic orders can be mechanistically informative. Fractional kinetic orders suggest dissociation of a dominant aggregate to give a smaller reactive species. An apparent negative kinetic order, due to competition with a second-order process, leads to spontaneous deracemization of chiral crystals. Changes in bond dissociation energies can be due to differences in bonds or in radicals. Although it is often said that the order of alkyl radical stability is tertiary > secondary > primary, careful analysis suggests that the order of bond dissociation energies may be due to differences in the alkanes rather than in the radicals. Hammond helped organic chemists begin to think systematically about predicting relative reaction rates by suggesting that the transition states of more exothermic reactions should lie closer to the starting materials in structure and energy.
关 键 词: 聚集体离解; 键离解能; 相对反应速率
课程来源: 视频讲座网
数据采集: 2021-11-13:zkj
最后编审: 2021-11-13:zkj
阅读次数: 58