Photoreactions of Sc3N@Ih-C80 and Lu3N@Ih-C80 with disilirane: Isolation and characterization of labile 1,2-adducts

IF 1.1 4区化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Heteroatom Chemistry Pub Date : 2018-12-18 DOI:10.1002/hc.21477

Masahiro Kako, Fumiaki Ozeki, Shinji Kanzawa, Shinpei Fukazawa, Kumiko Sato, Michio Yamada, Yutaka Maeda, Makoto Furukawa, Takeshi Akasaka

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引用次数: 2

Abstract

The photolysis of Sc₃N@I_h-C₈₀ with disilirane (1,2-disilacyclopropane) afforded the corresponding 1,2- and 1,4-adducts. The relatively unstable 1,2-product was characterized using spectroscopic and electrochemical analyses, and theoretical calculations. The relative energies of the optimized structures are consistent with the experimentally observed isomerization of the 1,2-adduct to the 1,4-adduct. The electron-donating effects of the silyl groups in these products were confirmed by comparing the redox potentials of the related Sc₃N@I_h-C₈₀ derivatives. The relative stabilities and electronic properties of the 1,2- and 1,4-adducts of Lu₃N@I_h-C₈₀ show similar aspects to those obtained for the corresponding Sc₃N@I_h-C₈₀ derivatives.

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Sc3N@I h -C80和Lu3N@I h -C80与二硅烷的光化学反应:不稳定1,2加合物的分离和表征

Sc3N@Ih-C80与二硅烷(1,2-二硅环丙烷)光解得到相应的1,2-和1,4-加合物。利用光谱和电化学分析以及理论计算对相对不稳定的1,2-产物进行了表征。优化结构的相对能与实验观察到的1,2-加合物到1,4-加合物的异构化一致。通过比较相关Sc3N@Ih-C80衍生物的氧化还原电位，证实了这些产物中硅基的给电子作用。Lu3N@Ih-C80的1,2-和1,4-加合物的相对稳定性和电子性质与相应的Sc3N@Ih-C80衍生物相似。

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来源期刊

Heteroatom Chemistry 化学-化学综合

CiteScore

1.20

自引率

0.00%

发文量

审稿时长

6 months

期刊介绍： Heteroatom Chemistry brings together a broad, interdisciplinary group of chemists who work with compounds containing main-group elements of groups 13 through 17 of the Periodic Table, and certain other related elements. The fundamental reactivity under investigation should, in all cases, be concentrated about the heteroatoms. It does not matter whether the compounds being studied are acyclic or cyclic; saturated or unsaturated; monomeric, polymeric or solid state in nature; inorganic, organic, or naturally occurring, so long as the heteroatom is playing an essential role. Computational, experimental, and combined studies are equally welcome. Subject areas include (but are by no means limited to): -Reactivity about heteroatoms for accessing new products or synthetic pathways -Unusual valency main-group element compounds and their properties -Highly strained (e.g. bridged) main-group element compounds and their properties -Photochemical or thermal cleavage of heteroatom bonds and the resulting reactivity -Uncommon and structurally interesting heteroatom-containing species (including those containing multiple bonds and catenation) -Stereochemistry of compounds due to the presence of heteroatoms -Neighboring group effects of heteroatoms on the properties of compounds -Main-group element compounds as analogues of transition metal compounds -Variations and new results from established and named reactions (including Wittig, Kabachnik–Fields, Pudovik, Arbuzov, Hirao, and Mitsunobu) -Catalysis and green syntheses enabled by heteroatoms and their chemistry -Applications of compounds where the heteroatom plays a critical role. In addition to original research articles on heteroatom chemistry, the journal welcomes focused review articles that examine the state of the art, identify emerging trends, and suggest future directions for developing fields.