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氮杂环卡宾镍（0）配合物介导的白磷聚集与降解

Aggregation and Degradation of White Phosphorus Mediated by N-Heterocyclic Carbene Nickel(0) Complexes.

作者信息

Hierlmeier Gabriele, Coburger Peter, van Leest Nicolaas P, de Bruin Bas, Wolf Robert

机构信息

Universität Regensburg, Institut für Anorganische Chemie, 93040, Regensburg, Germany.

University of Amsterdam, van 't Hoff Institute for Molecular Sciences, Science Park 904, 1098 XH, Amsterdam, The Netherlands.

出版信息

Angew Chem Int Ed Engl. 2020 Aug 10;59(33):14148-14153. doi: 10.1002/anie.202004020. Epub 2020 Jun 3.

DOI:10.1002/anie.202004020
PMID:32348622
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC7496536/
Abstract

The reaction of zerovalent nickel compounds with white phosphorus (P ) is a barely explored route to binary nickel phosphide clusters. Here, we show that coordinatively and electronically unsaturated N-heterocyclic carbene (NHC) nickel(0) complexes afford unusual cluster compounds with P , P , P and P units. Using [Ni(IMes) ] [IMes=1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene], electron-deficient Ni P and Ni P clusters have been isolated, which can be described as superhypercloso and hypercloso clusters according to the Wade-Mingos rules. Use of the bulkier NHC complexes [Ni(IPr) ] or [(IPr)Ni(η -toluene)] [IPr=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene] affords a closo-Ni P cluster. Inverse-sandwich complexes [(NHC) Ni P ] (NHC=IMes, IPr) with an aromatic cyclo-P ligand were identified as additional products.

摘要

零价镍化合物与白磷（P₄）的反应是制备二元磷化镍簇合物鲜有人探索的途径。在此，我们表明配位和电子不饱和的N-杂环卡宾（NHC）镍（0）配合物能与P₄生成不同寻常的簇合物，含有P₂、P₃和P₄单元。使用[Ni(IMes)₂] [IMes = 1,3-双（2,4,6-三甲基苯基）咪唑啉-2-亚基]，已分离出缺电子的Ni₂P和Ni₃P簇合物，根据韦德-明戈斯规则，它们可被描述为超超闭合型和超闭合型簇合物。使用体积更大的NHC配合物[Ni(IPr)₂] 或[(IPr)Ni(η⁶-甲苯)] [IPr = 1,3-双（2,6-二异丙基苯基）咪唑啉-2-亚基]可得到闭合型Ni₃P簇合物。具有芳环P₃配体的反夹心配合物[(NHC)₂Ni₂P₂]（NHC = IMes、IPr）被鉴定为额外产物。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fb5c/7496536/9ca366eb8baa/ANIE-59-14148-g006.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fb5c/7496536/7f19900cbf03/ANIE-59-14148-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fb5c/7496536/53681b91bf42/ANIE-59-14148-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fb5c/7496536/de3bd6de184c/ANIE-59-14148-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fb5c/7496536/80fb94525152/ANIE-59-14148-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fb5c/7496536/d5cc8ffb70e0/ANIE-59-14148-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fb5c/7496536/9ca366eb8baa/ANIE-59-14148-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fb5c/7496536/6d64a9d80070/ANIE-59-14148-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fb5c/7496536/326ccd598c7f/ANIE-59-14148-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fb5c/7496536/7f19900cbf03/ANIE-59-14148-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fb5c/7496536/53681b91bf42/ANIE-59-14148-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fb5c/7496536/de3bd6de184c/ANIE-59-14148-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fb5c/7496536/80fb94525152/ANIE-59-14148-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fb5c/7496536/d5cc8ffb70e0/ANIE-59-14148-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fb5c/7496536/9ca366eb8baa/ANIE-59-14148-g006.jpg

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