Theoretical Study on the Structural-Function Relationship of Manganese(III)-Iodosylarene Adducts
Theoretical Study on the Structural-Function Relationship of Manganese(III)-Iodosylarene Adducts
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锰(III)-碘代芳烃加合物结构-功能关系的理论研究
DOI：
10.3389/fchem.2020.00744
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发表时间：
2020-08
影响因子：
5.5
通讯作者：
Yong Wang
中科院分区：
文献类型：
--
作者：
Dongru Sun;Xiaolu Chen;Lanping Gao;Yufen Zhao;Yong Wang
金属-碘代芳烃络合物最近被认为是与众所周知的高价金属-含氧物种一起的第二氧化剂。人们对各种金属-碘代芳烃配合物的结构-功能关系进行了广泛的研究。本文采用密度泛函理论计算研究了锰-碘酰苯配合物[MnIII（TBDAP）（PhIO）（OH）]2+（1）的这种关系。我们的结果符合实验观察，并揭示了新的机制的发现。1在磺基氧化反应中作为逐步的1 e +1 e氧化剂。令人惊讶的是，9，10-二氢蒽（DHA）的C-H键活化1通过一种新的离子氢化物转移/质子转移（HT/PT）机制进行。作为与1的比较，研究了碘酰苯单体PhIO的亲电性。PhIO在磺基氧化和C-H活化中进行协同的2 e-氧化。DHA的羟基化PhIO被发现进行通过一种新的离子和协调质子转移/羟基反弹机制，涉及2 e-氧化，形成一个短暂的碳物种。
Metal-iodosylarene complexes have been recently viewed as a second oxidant alongside of the well-known high-valent metal-oxo species. Extensive efforts have been exerted to unveil the structure-function relationship of various metal-iodosylarene complexes. In the present manuscript, density functional theoretical calculations were employed to investigate such relationship of a specific manganese-iodosylbenzene complex [MnIII(TBDAP)(PhIO)(OH)]2+ (1). Our results fit the experimental observations and revealed new mechanistic findings. 1 acts as a stepwise 1e+1e oxidant in sulfoxidation reactions. Surprisingly, C-H bond activation of 9,10-dihydroanthracene (DHA) by 1 proceeds via a novel ionic hydride transfer/proton transfer (HT/PT) mechanism. As a comparison to 1, the electrophilicity of an iodosylbenzene monomer PhIO was investigated. PhIO performs concerted 2e-oxidations both in sulfoxidation and C-H activation. Hydroxylation of DHA by PhIO was found to proceed via a novel ionic and concerted proton-transfer/hydroxyl-rebound mechanism involving 2e-oxidation to form a transient carbonium species.
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影响因子：
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作者：
Yang T;Quesne MG;Neu HM;Cantú Reinhard FG;Goldberg DP;de Visser SP
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影响因子：
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通讯作者：
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作者：
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