Real-Time In Situ Observation of Chemical Reactions

Real-Time In Situ Observation of Chemical Reactions
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实时原位观察化学反应

DOI:
10.1107/s0108767398009118
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发表时间:
1998
期刊:
Acta Crystallographica Section A
影响因子:
--
通讯作者:
Y. Ohashi
Y. Ohashi
中科院分区:
--
文献类型:
--
作者:
Y. Ohashi

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如果在反应过程中保持单晶的完整性,则可以通过分步晶体结构分析来观察晶体中的化学反应过程。这样的反应被称为“晶态反应”,逐步的晶体结构分析被称为“实时原位观察”。简要介绍了五个实时原位观察晶态反应的实例。第一个例子是通过用可见光照射来光学富集外消旋晶体。第二个例子是通过中子衍射原位观察氢氘交换。第三个例子是在可见光下直接观察到大体积手性基团的两步反转。第四个例子是通过可见光照射实时观察从3-氰基丙基到1-氰基丙基的两步异构化。第五个例子是氧分子插入过度拥挤的二苯乙烯化合物的反应。在所有的例子中,反应机理都是通过实时原位观察来阐明的,这是分析化学反应机理的有力手段。
The process of chemical reaction in a crystal can be observed by stepwise crystal structure analysis if the single-crystal integrity is preserved during the reaction. Such a reaction is called a 'crystalline-state reaction' and the stepwise crystal structure analysis is termed 'real-time in situ observation'. Five examples of real-time in situ observation of crystalline-state reactions are briefly described. The first example is the optical enrichment of a racemic crystal by irradiation with visible light. The second example is in situ observation of hydrogen-deuterium exchange by neutron diffraction. The third example is the direct observation of the two-step inversion of a bulky chiral group on exposure to visible light. The fourth example is the real-time observation of two-step isomerization from a 3-cyanopropyl group to a 1-cyanopropyl group by irradiation with visible light. The fifth example is the insertion reaction of an oxygen molecule into an overcrowded distibene compound. In all the examples, the reaction mechanisms are clarified by the real-time in situ observation, which is a powerful method to analyze the mechanism of chemical reactions.