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低聚硅烷基硅氮烷及其相关衍生物的电子转移与修饰

Electron Transfer and Modification of Oligosilanylsilatranes and Related Derivatives.

作者信息

Aghazadeh Meshgi Mohammad, Baumgartner Judith, Jouikov Viatcheslav V, Marschner Christoph

机构信息

Institut für Anorganische Chemie, Technische Universität Graz , Stremayrgasse 9, 8010 Graz, Austria.

Institut für Chemie, Universität Graz , Stremayrgasse 9, 8010 Graz, Austria.

出版信息

Organometallics. 2017 Jan 23;36(2):342-351. doi: 10.1021/acs.organomet.6b00786. Epub 2016 Dec 20.

DOI:10.1021/acs.organomet.6b00786
PMID:28133409
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5264216/
Abstract

Several silatranyl -substituted oligosilanes were prepared starting from bis(trimethylsilyl)silatranylsilanide. Electrochemical and theoretical investigations of some oligosilanes revealed that electrooxidation occurs by formation of a short-lived cation radical. This species undergoes structural relaxation to form a pair of conformers, with endo and exo relationships with respect to the Si-N interaction. Reaction of a 1,4-disilatranyl-1,4-disilanide with 1,2-dichlorotetramethyldisilane gave a mixture of cis and trans diastereomers of a cyclohexasilane with the trans isomer showing a diminished Si-N distance.

摘要

从双（三甲基硅基）硅杂氮硅三环硅烷出发制备了几种硅杂氮硅三环取代的低聚硅烷。对一些低聚硅烷的电化学和理论研究表明，电氧化是通过形成短寿命的阳离子自由基发生的。该物种经历结构弛豫形成一对构象异构体，相对于Si-N相互作用具有内型和外型关系。1,4-二硅杂氮硅三环-1,4-二硅烷与1,2-二氯四甲基二硅烷反应得到环己硅烷的顺式和反式非对映异构体混合物，其中反式异构体的Si-N距离减小。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cf6f/5264216/95f75280cab3/om-2016-007867_0010.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cf6f/5264216/b84b63b71103/om-2016-007867_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cf6f/5264216/3814014dc43f/om-2016-007867_0011.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cf6f/5264216/99d23646dd47/om-2016-007867_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cf6f/5264216/7c93acc21d1f/om-2016-007867_0012.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cf6f/5264216/1e4cd11bec03/om-2016-007867_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cf6f/5264216/7e057c44799c/om-2016-007867_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cf6f/5264216/332fc1b65a91/om-2016-007867_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cf6f/5264216/34b0cf934a81/om-2016-007867_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cf6f/5264216/d21d417ac018/om-2016-007867_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cf6f/5264216/42c8ddfcf39e/om-2016-007867_0008.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cf6f/5264216/95f75280cab3/om-2016-007867_0010.jpg

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