Organic chemistry as representation.

Organic chemistry as representation.
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DOI:
10.1007/s10698-020-09379-z
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发表时间:
2021-04
影响因子:
0.9
通讯作者:
Healy EF
Healy EF
中科院分区:
化学3区
文献类型:
--
作者:
Healy EF

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电子再分布是我们理解化学反应性的基石。对于绝大多数有机反应,电子被假定成对移动,通过中间结构的产生提供解释机制。但对于许多转换,这些离散的步骤是理想化的结构,涉及假设的中间体,但没有经验证明。这种以弯曲箭头形式主义为前提的统一观点导致了这样一种情景,即对于许多有机变换,我们假定的理解远远超过了我们不断增长的知识。重新制定有机机制,包括单电子转移(SET)作为一个组成部分,或替代,流行的图标描述可以提供一个更充分的经验机制的描述。此外,使用SET的语言提供了一个机会,统一机制的概念下一个共同的捐助者/接受者的框架。
Electron redistribution is the cornerstone of our understanding of chemical reactivity. For the vast majority of organic reactions electrons are assumed to move in pairs providing explanatory mechanisms through the generation of intermediate structures. But for many transformations these discrete steps are idealized constructs, involving intermediates assumed but not empirically justified. This unitary perspective predicated on the curved arrow formalism has resulted in the scenario where for many organic transformations our supposed understanding far surpasses our growing knowledge. Reformulating organic mechanisms to include single electron transfer (SET) as a component of, or an alternative to, the prevailing iconic descriptions can provide for a more empirically adequate mechanistic description. In addition using the language of SET presents an opportunity to unify mechanistic concepts under a common donor/acceptor framework.
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