Transition-state geometry measurements from (13)c isotope effects. The experimental transition state for the epoxidation of alkenes with oxaziridines.
Transition-state geometry measurements from (13)c isotope effects. The experimental transition state for the epoxidation of alkenes with oxaziridines.
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(13)c 同位素效应的过渡态几何测量。烯烃与氧氮丙啶环氧化的实验过渡态。
DOI：
10.1021/ja8088636
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发表时间：
2009-02-18
影响因子：
15
通讯作者：
Singleton DA
中科院分区：
文献类型：
--
作者：
Hirschi JS;Takeya T;Hang C;Singleton DA
我们建议并评估一种由理论计算和实验测量的13C动力学同位素效应相结合来测量特定原子间距离的方法。这一过程利用了可用于2-甲基-2-丁烯与恶唑烷环氧化反应的多种过渡结构。根据对这些过渡结构计算的同位素效应，建立了新形成键的C-O键距与同位素效应之间的理论独立关系。在测量精度范围内，这个关系结合实验的同位素效应，提供了在过渡态形成的C-O键的高度精确的图像。过渡态结构的多样性也允许根据非定常点的计算对定义过渡态几何的Schramm过程进行评估，该方法被发现是相当准确的。
We suggest here and evaluate a methodology for the measurement of specific interatomic distances from a combination of theoretical calculations and experimentally measured 13C kinetic isotope effects. This process takes advantage of a broad diversity of transition structures available for the epoxidation of 2-methyl-2-butene with oxaziridines. From the isotope effects calculated for these transition structures, a theory-independent relationship between the C-O bond distances of the newly forming bonds and the isotope effects is established. Within the precision of the measurement, this relationship in combination with the experimental isotope effects provides a highly accurate picture of the C-O bonds forming at the transition state. The diversity of transition structures also allows an evaluation of the Schramm process for defining transition state geometries based on calculations at non-stationary points, and the methodology is found to be reasonably accurate.
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影响因子：
1.8
作者：
BAUMSTARK, AL;MCCLOSKEY, CJ
通讯作者：
MCCLOSKEY, CJ
影响因子：
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作者：
BACH, RD;ANDRES, JL;DAVIS, FA
通讯作者：
DAVIS, FA
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15
作者：
Houk, KN;Liu, J;Condroski, KR
通讯作者：
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作者：
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作者：
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通讯作者：
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