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钴和铁稳定的羰游基、酮亚胺基和醛亚胺基自由基阴离子。

Cobalt and Iron Stabilized Ketyl, Ketiminyl and Aldiminyl Radical Anions.

作者信息

Sieg Grégoire, Pessemesse Quentin, Reith Sascha, Yelin Stefan, Limberg Christian, Munz Dominik, Werncke C Gunnar

机构信息

Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35043, Marburg, Germany.

Univ. Lyon, ENS de Lyon, CNRS UMR 5182 Université Claude Bernard Lyon 1, Laboratoire de Chimie, 69342, Lyon, France.

出版信息

Chemistry. 2021 Dec 1;27(67):16760-16767. doi: 10.1002/chem.202103096. Epub 2021 Oct 22.

DOI:10.1002/chem.202103096
PMID:34569676
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9298351/
Abstract

Carbonyl and iminyl based radical anions are reactive intermediates in a variety of transformations in organic synthesis. Herein, the isolation of ketyl, and more importantly unprecedented ketiminyl and aldiminyl radical anions coordinated to cobalt and iron complexes is presented. Insights into the electronic structure of these unusual metal bound radical anions is provided by X-Ray diffraction analysis, NMR, IR, UV/Vis and Mössbauer spectroscopy, solid and solution state magnetometry, as well as a by a detailed computational analysis. The metal bound radical anions are very reactive and facilitate the activation of intra- and intermolecular C-H bonds.

摘要

基于羰基和亚胺基的自由基阴离子是有机合成中各种转化反应的活性中间体。本文介绍了酮基自由基阴离子的分离，更重要的是，还分离出了前所未有的与钴和铁配合物配位的酮亚胺基和醛亚胺基自由基阴离子。通过X射线衍射分析、核磁共振、红外光谱、紫外/可见光谱和穆斯堡尔光谱、固态和溶液态磁学测量以及详细的计算分析，对这些不同寻常的金属结合自由基阴离子的电子结构有了深入了解。金属结合自由基阴离子具有很高的反应活性，能够促进分子内和分子间C-H键的活化。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a9be/9298351/ab56dd2a2dc1/CHEM-27-16760-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a9be/9298351/21eb98d419c4/CHEM-27-16760-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a9be/9298351/0e3eeb9cb976/CHEM-27-16760-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a9be/9298351/8140a7ce4bbb/CHEM-27-16760-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a9be/9298351/599d17bc6e1b/CHEM-27-16760-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a9be/9298351/13fb3b3ddf87/CHEM-27-16760-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a9be/9298351/0f08ffc37d42/CHEM-27-16760-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a9be/9298351/88490acf8bbf/CHEM-27-16760-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a9be/9298351/b17d278bf495/CHEM-27-16760-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a9be/9298351/ab56dd2a2dc1/CHEM-27-16760-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a9be/9298351/21eb98d419c4/CHEM-27-16760-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a9be/9298351/0e3eeb9cb976/CHEM-27-16760-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a9be/9298351/8140a7ce4bbb/CHEM-27-16760-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a9be/9298351/599d17bc6e1b/CHEM-27-16760-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a9be/9298351/13fb3b3ddf87/CHEM-27-16760-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a9be/9298351/0f08ffc37d42/CHEM-27-16760-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a9be/9298351/88490acf8bbf/CHEM-27-16760-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a9be/9298351/b17d278bf495/CHEM-27-16760-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a9be/9298351/ab56dd2a2dc1/CHEM-27-16760-g006.jpg

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