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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Cycloreversion of Formylcyclobutane Radical Anion: Two-Step Rotating Mechanism
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Cycloreversion of Formylcyclobutane Radical Anion: Two-Step Rotating Mechanism

机译：甲酰基环丁烷自由基阴离子的环还原：两步旋转机理

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摘要

The [2+2] cycloreversion reaction of formylcyclobutane radical anion (c-C_4H_7-CHO~(·-)) has been investigated at the UB3LYP level with the augmented Dunning's correlation-consistent polarized valence double-ξ basis set supplied with four even-tempered sp shells. Very diffuse p-π*-like singly occupied orbitals (SOMO) are found for the c-C_4H_7-CHO~(·-) and product CH_2CHCHO~(·-) radical anions, necessitating the use of a rather diffuse basis set for mechanistic study. The respective electron affinities of c-C_4H_7-CHO and CH_2CHCHO are calculated to be 5.4 and 16.1 kcal/mol, showing the ability to bind an extra electron. The intermediate structure ·(CH_2)_3CHCHO~- is found to be a valence-bound distonic anion apt to the elimination of C_2H_4. The present two-step "rotating" cycloreversion mechanism for c-C_4H_7-CHO~(·-) is formally similar to the biradical one for neutral cyclobutane structures, but with evidently lower potential barrier. For efficient electron-attachment catalysis, the extra electron should be trapped by suitable functional groups in some orbitals with substantial overlap with the σ*-orbitals of the cyclobutane structure.
机译：已在UB3LYP水平上研究了甲酰基环丁烷自由基阴离子（c-C_4H_7-CHO〜（·-））的[2 + 2]环还原反应，并使用增强的Dunning的相关一致极化价双-ξ基组提供了四个偶数-淬火的sp壳。对于c-C_4H_7-CHO〜（·-）和产物CH_2CHCHO〜（·-）自由基阴离子，发现了非常弥散的类似p-π*的单占据轨道（SOMO），因此需要使用相当弥散的基集用于机理研究。计算出c-C_4H_7-CHO和CH_2CHCHO的电子亲和力分别为5.4和16.1 kcal / mol，显示了结合多余电子的能力。发现中间结构·（CH_2）_3CHCHO〜-是易于消除C_2H_4的价键结合的二元阴离子。当前的c-C_4H_7-CHO〜（·-）两步“旋转”环还原机理在形式上类似于中性环丁烷结构的双自由基，但势垒明显降低。为了有效地进行电子附着催化，多余的电子应被合适的官能团捕获在某些与环丁烷结构的σ*轨道基本重叠的轨道中。

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