Computational studies on exothermic carbon–carbon bond cleavages

IF 1.9 4区 化学 Q2 CHEMISTRY, ORGANIC Journal of Physical Organic Chemistry Pub Date : 2024-03-26 DOI:10.1002/poc.4606
Athanassios Nicolaides, Hideo Tomioka
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Abstract

Structural aspects of single CC bond dissociation energies are examined and it is shown that in certain cases a negative bond dissociation energy (BDE) implies a very weak bond and an unstable species prone to bond breaking resulting in dissociation or structural rearrangement. It is proposed that, in such cases, a better quantitative indicator for the strength of the bond is the activation energy required for its fission. o-Phenelylene bis(nitrene) 1 is computed to have the most negative CC BDE for an observable species. Under cryogenic conditions, activation energy for the dissociation of this bond has been measured as only 2.8 kcal/mol, making it the weakest that we know of. An explanation based on the formation of two new bonds as responsible for this extremely weak bond is given.

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碳-碳键裂解放热计算研究
研究了单 CC 键离解能的结构方面,结果表明,在某些情况下,负键离解能(BDE)意味着键非常弱,是一种不稳定的物质,容易断键导致离解或结构重排。根据计算,邻苯乙烯双(腈)1 在可观察到的物种中具有最负的 CC BDE。在低温条件下,该键解离的活化能仅为 2.8 kcal/mol,是我们所知的最弱的键。我们给出的解释是,这种极弱的键是由两个新键的形成造成的。
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来源期刊
CiteScore
3.60
自引率
11.10%
发文量
161
审稿时长
2.3 months
期刊介绍: The Journal of Physical Organic Chemistry is the foremost international journal devoted to the relationship between molecular structure and chemical reactivity in organic systems. It publishes Research Articles, Reviews and Mini Reviews based on research striving to understand the principles governing chemical structures in relation to activity and transformation with physical and mathematical rigor, using results derived from experimental and computational methods. Physical Organic Chemistry is a central and fundamental field with multiple applications in fields such as molecular recognition, supramolecular chemistry, catalysis, photochemistry, biological and material sciences, nanotechnology and surface science.
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