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通过暴露的、多重键合的铁（III）氧代配合物进行的烃类氧化反应。

Hydrocarbon Oxidation by an Exposed, Multiply Bonded Iron(III) Oxo Complex.

作者信息

Valdez-Moreira Juan A, Beagan Daniel M, Yang Hao, Telser Joshua, Hoffman Brian M, Pink Maren, Carta Veronica, Smith Jeremy M

机构信息

Department of Chemistry, Indiana University, 800 E. Kirkwood Avenue, Bloomington Indiana 47405, United States.

Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States.

出版信息

ACS Cent Sci. 2021 Oct 27;7(10):1751-1755. doi: 10.1021/acscentsci.1c00890. Epub 2021 Sep 23.

DOI:10.1021/acscentsci.1c00890
PMID:34729418
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC8554833/
Abstract

The iron oxo unit, [Fe=O] is a critical intermediate in biological oxidation reactions. While its higher oxidation states are well studied, relatively little is known about the least-oxidized form [Fe=O]. Here, the thermally stable complex PhB(AdIm)Fe=O has been structurally, spectroscopically, and computationally characterized as a iron(III) oxo. An unusually short Fe-O bond length is consistent with iron-oxygen multiple bond character and is supported by electronic structure calculations. The complex is thermally stable yet is able to perform hydrocarbon oxidations, facilitating both C-O bond formation and dehydrogenation reactions.

摘要

铁氧单元[Fe=O]是生物氧化反应中的关键中间体。虽然其较高氧化态已得到充分研究，但对于氧化程度最低的形式[Fe=O]却知之甚少。在此，热稳定配合物PhB(AdIm)Fe=O已通过结构、光谱和计算表征为铁(III)氧代物。异常短的Fe-O键长与铁-氧多重键特征一致，并得到电子结构计算的支持。该配合物热稳定，但能够进行烃类氧化反应，促进C-O键形成和脱氢反应。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/61c6/8554833/396f9267c7cb/oc1c00890_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/61c6/8554833/bba3672b909b/oc1c00890_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/61c6/8554833/b085d92812ae/oc1c00890_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/61c6/8554833/d9a58e5c0e1f/oc1c00890_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/61c6/8554833/b0511198af5f/oc1c00890_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/61c6/8554833/8558287d6172/oc1c00890_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/61c6/8554833/776cff9c811f/oc1c00890_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/61c6/8554833/396f9267c7cb/oc1c00890_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/61c6/8554833/bba3672b909b/oc1c00890_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/61c6/8554833/b085d92812ae/oc1c00890_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/61c6/8554833/d9a58e5c0e1f/oc1c00890_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/61c6/8554833/b0511198af5f/oc1c00890_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/61c6/8554833/8558287d6172/oc1c00890_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/61c6/8554833/776cff9c811f/oc1c00890_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/61c6/8554833/396f9267c7cb/oc1c00890_0007.jpg

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