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可分离的三配位碱稳定亚铝烯：无受体持久性单体氧化铝的前体。

Isolable Three-Coordinate Base-Stabilized Alumylene: A Precursor of Persistent Acceptor-Free Monomeric Aluminum Oxide.

作者信息

Baeza José Miguel León, Xu Huihui, Takahashi Shintaro, Baceiredo Antoine, Guerrero Rene Segundo Rojas, Hashizume Daisuke, Saffon-Merceron Nathalie, Branchadell Vicenç, Kato Tsuyoshi

机构信息

Laboratoire Hétérochimie Fondamentale et Appliquée (UMR 5069), Université de Toulouse, CNRS, 118 route de Narbonne, Toulouse, F-31062, France.

Departamento de Química Inorgánica, Facultad de Química y de Farmacia, Pontificia Universidad Católica de Chile, Casilla 306, Santiago 22, Chile.

出版信息

Angew Chem Int Ed Engl. 2025 Jun 2;64(23):e202505181. doi: 10.1002/anie.202505181. Epub 2025 Apr 10.

DOI:10.1002/anie.202505181
PMID:40162864
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC12124428/
Abstract

An isolable monomeric alumylene 2 stabilized by two donating ligands (phosphine and NHC) has been synthesized. Experimental and theoretical analysis confirm that the NHC ligand in 2 is labile and reversibly dissociates from the Al center above -20 °C. Of particular interest, despite being thermodynamically stabilized by two donor ligands, alumylene complex 2 exhibits a high reactivity with a considerably higher nucleophilicity compared to the monophosphine-ligated complex 5. It is interesting to note that 2 reacts immediately with NO at -90 °C, allowing the synthesis of bis-ligated aluminum oxide 15, which is stable up to -70 °C.

摘要

一种由两个给体配体（膦和NHC）稳定的可分离单体亚铝烯2已被合成。实验和理论分析证实，2中的NHC配体不稳定，在-20℃以上会从铝中心可逆解离。特别值得注意的是，尽管亚铝烯配合物2通过两个给体配体在热力学上得到稳定，但与单膦配位的配合物5相比，它表现出高得多的反应活性和相当高的亲核性。值得注意的是，2在-90℃下立即与NO反应，从而能够合成双配位氧化铝15，其在-70℃以下是稳定的。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f001/12124428/64b83f8d2f78/ANIE-64-e202505181-g010.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f001/12124428/6c53fec282f8/ANIE-64-e202505181-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f001/12124428/a5c04f97205f/ANIE-64-e202505181-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f001/12124428/23f37926d774/ANIE-64-e202505181-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f001/12124428/37708127500d/ANIE-64-e202505181-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f001/12124428/eb372da79e0e/ANIE-64-e202505181-g004.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f001/12124428/64b83f8d2f78/ANIE-64-e202505181-g010.jpg

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