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高价非氧合钴（IV）和形式上的钴（V）配合物的制备、光谱表征及反应活性

Preparation, Spectroscopic Characterization, and Reactivity of High-Valent Non-Oxo Co(IV) and Formally Co(V) Complexes.

作者信息

Yang Jindou, Larson Virginia A, Castella Daniel G, Wilson Devin F, Xing Ying, Seo Mi Sook, Lee Yong-Min, Slobin Ava Grace, Fukuzumi Shunichi, Shearer Jason, Lehnert Nicolai, Nam Wonwoo

机构信息

Department of Chemistry and Nano Science, Ewha Womans University, Seoul 03760, Korea.

Department of Chemistry and Department of Biophysics, University of Michigan, Ann Arbor, Michigan 48109-1055, United States.

出版信息

JACS Au. 2025 Jul 15;5(7):3575-3588. doi: 10.1021/jacsau.5c00589. eCollection 2025 Jul 28.

DOI:10.1021/jacsau.5c00589
PMID:40747019
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC12308381/
Abstract

In the presence of artificial oxidants, high-valent Co-X (X = O and NTs) complexes can be achieved in many different types of ligand structures. This paper reports, for the first time, the synthesis, spectroscopic and theoretical characterization, and reactivity of formally Co-(V) and Co-(IV) intermediates without the axial oxo or imido groups by using a strongly electron-donating ligand, PCAPD (PCAPD = bis-[2-(1H-pyrrol-2-carboxamido)--phenylenediamine). The formally Co-(V) complex was prepared by reacting [EtN][Co(PCAPD)-(Cl)] with iodosylbenzene (PhIO) as an artificial oxidant in acetone at -40 °C. Then, the formally Co-(V) complex was characterized with various spectroscopic methods, such as EPR, CSI-MS, MCD, XAS, and EXAFS, revealing a diamagnetic [Co(PCAPD)-(OH)] species with a Co-(IV) ion and one-electron oxidized coligand. Here, EXAFS shows a six-coordinate complex, likely with axial hydroxide ligands, but no oxo group with a short Co-X vector. This species can be further one-electron reduced by MeFc to afford [Co(PCAPD)-(OH)] in frozen conditions. EPR and MCD measurements show that [Co(PCAPD)-(OH)] has an = 1/2 ground state with a Co-(IV) center according to XAS. EXAFS shows essentially identical ligand environments about the Co center in [Co(PCAPD)-(OH)] and [Co(PCAPD)-(OH)]. Remarkably, the exact same high-valent species can be generated when [EtN][Co(PCAPD)-(Cl)] is oxidized with -tosyliminophenyliodinane (PhINTs). The reactivity of [Co(PCAPD)-(OH)] was further investigated in hydrogen atom and oxygen atom transfer reactions, revealing that the reactivity of [Co(PCAPD)-(OH)] is much lower than that of other Co-X species.

摘要

在人工氧化剂存在的情况下，高价钴-X（X = O和NTs）配合物可以在许多不同类型的配体结构中实现。本文首次报道了通过使用强供电子配体PCAPD（PCAPD = 双-[2-(1H-吡咯-2-甲酰胺基)-对苯二胺]）合成、光谱和理论表征以及无轴向氧代或亚氨基的形式上的Co-(V)和Co-(IV)中间体的反应活性。形式上的Co-(V)配合物是通过在-40°C的丙酮中使[EtN][Co(PCAPD)-(Cl)]与作为人工氧化剂的碘苯（PhIO）反应制备的。然后，用各种光谱方法对形式上的Co-(V)配合物进行了表征，如电子顺磁共振（EPR）、碰撞诱导解离质谱（CSI-MS）、磁圆二色性（MCD）、X射线吸收光谱（XAS）和扩展X射线吸收精细结构（EXAFS），揭示了一种抗磁性的[Co(PCAPD)-(OH)]物种，其含有一个Co-(IV)离子和一个单电子氧化的共配体。在此，EXAFS显示出一种六配位配合物，可能带有轴向氢氧化物配体，但没有具有短Co-X向量的氧代基团。在冷冻条件下，该物种可以被二茂铁甲基（MeFc）进一步单电子还原为[Co(PCAPD)-(OH)]。EPR和MCD测量表明，根据XAS，[Co(PCAPD)-(OH)]具有一个基态为S = 1/2的Co-(IV)中心。EXAFS显示[Co(PCAPD)-(OH)]和[Co(PCAPD)-(OH)]中Co中心周围的配体环境基本相同。值得注意的是，当用对甲苯磺酰亚氨基苯碘鎓（PhINTs）氧化[EtN][Co(PCAPD)-(Cl)]时，可以生成完全相同的高价物种。进一步研究了[Co(PCAPD)-(OH)]在氢原子和氧原子转移反应中的反应活性，结果表明[Co(PCAPD)-(OH)]的反应活性远低于其他Co-X物种。

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