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室温下通过可逆的分子内插入芳环 C-C 键实现 Si(IV)和 Si(II)之间的互变。

Room-Temperature-Observable Interconversion Between Si(IV) and Si(II) via Reversible Intramolecular Insertion Into an Aromatic C-C Bond.

机构信息

School of Natural Sciences, Department of Chemistry WACKER-Institute of Silicon Chemistry and Catalysis Research Centre Technical University of Munich, Lichtenbergstraße 4, 85748, Garching bei München, Germany.

出版信息

Chemistry. 2022 Dec 9;28(69):e202202330. doi: 10.1002/chem.202202330. Epub 2022 Oct 19.

DOI:10.1002/chem.202202330
PMID:36098491
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC10092829/
Abstract

An easily isolable silacycloheptatriene (silepin) 1 b was synthesized from the reaction of a N-heterocyclic imino (IPrN) substituted tribromosilane IPrNSiBr with the sterically congested bis(trimethylsilyl)triisopropylsilyl silanide KSi(TMS) Si( Pr) (BTTPS). In solution, the Si(IV) silepin 1 b is in a thermodynamic equilibrium with the acyclic Si(II) silylene 1 a. The relative concentration of the Si(II) or Si(IV) isomers can be controlled by temperature variation and observed by variable temperature NMR and UV/Vis spectroscopy. DFT calculations show a small reaction barrier for the Si(II)⇌Si(IV) interconversion and a small energy gap between the Si(II) and Si(IV) species. The reactivity of 1 a/b is demonstrated on a variety of small molecules.

摘要

一种易于分离的硅杂环庚三烯（silepin）1b 是通过 N-杂环亚氨基（IPrN）取代的三溴硅烷 IPrNSiBr 与空间位阻较大的双（三甲基硅基）三异丙基甲硅烷基二硅烷 KSi(TMS) Si(Pr) (BTTPS)反应得到的。在溶液中，Si(IV) 硅杂环庚三烯 1b 处于与无环 Si(II) 硅烯 1a 的热力学平衡状态。Si(II) 或 Si(IV) 异构体的相对浓度可以通过温度变化来控制，并通过变温 NMR 和 UV/Vis 光谱进行观察。DFT 计算表明 Si(II) ⇌ Si(IV) 互变异构的反应势垒较小，Si(II) 和 Si(IV) 物种之间的能隙较小。1a/b 的反应性在各种小分子上得到了证明。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/97b0/10092829/de574def057e/CHEM-28-0-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/97b0/10092829/d32cbe38d113/CHEM-28-0-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/97b0/10092829/c0825deebf08/CHEM-28-0-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/97b0/10092829/4091cbc40b68/CHEM-28-0-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/97b0/10092829/08f2457b73d2/CHEM-28-0-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/97b0/10092829/8f5c406470c0/CHEM-28-0-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/97b0/10092829/eddd47fe55a6/CHEM-28-0-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/97b0/10092829/f7101abe6349/CHEM-28-0-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/97b0/10092829/6d35ebe3cf56/CHEM-28-0-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/97b0/10092829/de574def057e/CHEM-28-0-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/97b0/10092829/d32cbe38d113/CHEM-28-0-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/97b0/10092829/c0825deebf08/CHEM-28-0-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/97b0/10092829/4091cbc40b68/CHEM-28-0-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/97b0/10092829/08f2457b73d2/CHEM-28-0-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/97b0/10092829/8f5c406470c0/CHEM-28-0-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/97b0/10092829/eddd47fe55a6/CHEM-28-0-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/97b0/10092829/f7101abe6349/CHEM-28-0-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/97b0/10092829/6d35ebe3cf56/CHEM-28-0-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/97b0/10092829/de574def057e/CHEM-28-0-g009.jpg

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