{"title":"Photoreactions of Sc3N@Ih-C80 and Lu3N@Ih-C80 with disilirane: Isolation and characterization of labile 1,2-adducts","authors":"Masahiro Kako, Fumiaki Ozeki, Shinji Kanzawa, Shinpei Fukazawa, Kumiko Sato, Michio Yamada, Yutaka Maeda, Makoto Furukawa, Takeshi Akasaka","doi":"10.1002/hc.21477","DOIUrl":null,"url":null,"abstract":"<p>The photolysis of Sc<sub>3</sub>N@<i>I</i><sub><i>h</i></sub>-C<sub>80</sub> 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 Sc<sub>3</sub>N@<i>I</i><sub><i>h</i></sub>-C<sub>80</sub> derivatives. The relative stabilities and electronic properties of the 1,2- and 1,4-adducts of Lu<sub>3</sub>N@<i>I</i><sub><i>h</i></sub>-C<sub>80</sub> show similar aspects to those obtained for the corresponding Sc<sub>3</sub>N@<i>I</i><sub><i>h</i></sub>-C<sub>80</sub> derivatives.</p>","PeriodicalId":12816,"journal":{"name":"Heteroatom Chemistry","volume":"29 5-6","pages":""},"PeriodicalIF":1.1000,"publicationDate":"2018-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1002/hc.21477","citationCount":"2","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Heteroatom Chemistry","FirstCategoryId":"92","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/hc.21477","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 2
Abstract
The photolysis of Sc3N@Ih-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@Ih-C80 derivatives. The relative stabilities and electronic properties of the 1,2- and 1,4-adducts of Lu3N@Ih-C80 show similar aspects to those obtained for the corresponding Sc3N@Ih-C80 derivatives.
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.