Dioxygen Activation and Pyrrole α-Cleavage with Calix[4]pyrrolato Aluminates: Enzyme Model by Structural Constraint,Angewandte Chemie International Edition

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Dioxygen Activation and Pyrrole α-Cleavage with Calix[4]pyrrolato Aluminates: Enzyme Model by Structural Constraint
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2021-05-06 , DOI: 10.1002/anie.202104916
Lukas Maximilian Sigmund ₁ , Christopher Ehlert _{2,

3} , Markus Enders ₁ , Jürgen Graf ₄ , Ganna Gryn'ova _{2,

3} , Lutz Greb ₁

Affiliation

The present work describes the reaction of triplet dioxygen with the porphyrinogenic calix[4]pyrrolato aluminates to alkylperoxido aluminates in high selectivity. Multiconfigurational quantum chemical computations disclose the mechanism for this spin-forbidden process. Despite a negligible spin–orbit coupling constant, the intersystem crossing (ISC) is facilitated by singlet and triplet state degeneracy and spin–vibronic coupling. The formed peroxides are stable toward external substrates but undergo an unprecedented oxidative pyrrole α-cleavage by ligand aromatization/dearomatization-initiated O−O σ-bond scission. A detailed comparison of the calix[4]pyrrolato aluminates with dioxygen-related enzymology provides insights into the ISC of metal- or cofactor-free enzymes. It substantiates the importance of structural constraint and element–ligand cooperativity for the functions of aerobic life.

中文翻译：

用杯[4]吡咯酸铝酸盐激活分子氧和吡咯α-裂解：结构约束的酶模型

目前的工作描述了三线态分子氧与卟啉原杯[4]吡咯合铝酸盐以高选择性反应生成烷基过氧化铝酸盐。多构型量子化学计算揭示了这种自旋禁止过程的机制。尽管自旋-轨道耦合常数可以忽略不计，但单线态和三线态简并以及自旋-振动耦合促进了系统间交叉（ISC）。形成的过氧化物对外部底物是稳定的，但通过配体芳构化/脱芳构化引发的 O-O σ 键断裂经历了前所未有的氧化吡咯 α-裂解。杯 [4] 吡咯合铝酸盐与分子氧相关酶学的详细比较提供了对无金属或无辅因子酶的 ISC 的见解。

更新日期：2021-06-28

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