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快速通信:用于分子内C-H活化的受生物启发的配体框架的灵活性

Flash Communication: Flexibility of a Biologically Inspired Ligand Framework for Intramolecular C-H Activation.

作者信息

Moore Jewelianna M, Park Yun Ji, Fout Alison R

机构信息

Department of Chemistry, Texas A&M University, 580 Ross St. College Station, Texas 77843, United States.

School of Chemical Sciences, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, United States.

出版信息

Organometallics. 2025 Jan 17;44(3):472-476. doi: 10.1021/acs.organomet.4c00454. eCollection 2025 Feb 10.

Abstract

High-valent iron complexes play a crucial role in the oxidation of organic substrates, especially in C-H bond functionalization reactions in biology. This paper investigates the reactivity of nonporphyrin tripodal ligands featuring a secondary coordination sphere, focusing on their prospective ability to stabilize high-valent iron-oxo species. Using NMR spectroscopy and X-ray crystallography, we detail the formation of an Fe(III)-alkoxide complex through intramolecular C-H bond activation, providing insight into the potential transient formation of a high-valent iron-oxo intermediate. While attempts to observe an Fe(IV)-oxo complex were unsuccessful, our findings underscore the significance of the ligand electronic environment in stabilizing reactive iron species for C-H bond activation.

摘要

高价铁配合物在有机底物的氧化过程中起着至关重要的作用,尤其是在生物学中的C-H键官能化反应中。本文研究了具有二级配位球的非卟啉三脚架配体的反应活性,重点关注其稳定高价铁-氧物种的潜在能力。通过核磁共振光谱和X射线晶体学,我们详细阐述了通过分子内C-H键活化形成Fe(III)-醇盐配合物的过程,这为深入了解高价铁-氧中间体的潜在瞬态形成提供了线索。虽然观察Fe(IV)-氧配合物的尝试未成功,但我们的研究结果强调了配体电子环境在稳定用于C-H键活化的活性铁物种方面的重要性。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a624/11816012/45dad5ecd8de/om4c00454_0001.jpg

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