NDLI: Preparation, Structural Determination, and Characterization of Electronic Properties of Bis-silylated and Bis-germylated $Lu_{3}N@I_{h}-C_{80}$

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Preparation, Structural Determination, and Characterization of Electronic Properties of Bis-silylated and Bis-germylated $Lu_{3}N@I_{h}-C_{80}$

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Miyabe, Kyosuke Suzuki, Mitsuaki Maeda, Yutaka Wang, Wei-wei Yamada, Michio Akasaka, Takeshi Olmstead, Marilyn M. Sato, Kumiko Balch, Alan L. Kako, Masahiro Mizorogi, Naomi Nagase, Shigeru
Description	Author Affiliation: Kako M ( Department of Engineering Science, The University of Electro-Communications, Chofu 182-8585 (Japan). kako@e-one.uec.ac.jp.); Miyabe K ( Department of Engineering Science, The University of Electro-Communications, Chofu 182-8585 (Japan).); Sato K ( Life Science Center of Tsukuba Advanced Research Alliance, University of Tsukuba, Ibaraki 305-8577 (Japan).); Suzuki M ( Life Science Center of Tsukuba Advanced Research Alliance, University of Tsukuba, Ibaraki 305-8577 (Japan).); Mizorogi N ( Department of Chemistry, Tokyo Gakugei University, Tokyo 184-8501 (Japan).); Wang WW ( Life Science Center of Tsukuba Advanced Research Alliance, University of Tsukuba, Ibaraki 305-8577 (Japan).); Yamada M ( Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto 606-8103 (Japan).); Maeda Y ( Department of Chemistry, Tokyo Gakugei University, Tokyo 184-8501 (Japan).); Olmstead MM ( Department of Chemistry, Tokyo Gakugei University, Tokyo 184-8501 (Japan).); Balch AL ( Department of Chemistry, University of California, Davis, California 95616 (USA). mmolmstead@ucdavis.edu.); Nagase S ( Department of Chemistry, University of California, Davis, California 95616 (USA). albalch@ucdavis.edu.); Akasaka T ( Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto 606-8103 (Japan). nagase@ims.ac.jp.)
Abstract	Bis-silylated and bis-germylated derivatives of $Lu_{3}N@I_{h}-C_{80}$ (3, 4, 5) were successfully synthesized by the photochemical addition of disiliranes 1 a, 1 b or digermirane 2, and fully characterized by spectroscopic, electrochemical, and theoretical studies. Interestingly, digermirane 2 reacts more efficiently than disiliranes 1 a and 1 b because of its good electron-donor properties and lower steric hindrance around the GeGe bond. The 1,4-adduct structures of 3, 4, 5 were unequivocally established by single-crystal X-ray crystallographic analyses. The electrochemical and theoretical studies reveal that the energy gaps between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the 1,4-adducts are remarkably smaller than those of $Lu_{3}N@I_{h}-C_{80},$ because the electron-donating groups effectively raise the HOMO levels. It is also observed that germyl groups are slightly more electron-donating than the silyl groups on the basis of the redox properties and the HOMO–LUMO energies of 4 and 5. Bis-silylation and bis-germylation are effective and versatile methods for tuning the electronic characteristics of endohedral metallofullerenes.
ISSN	09476539
e-ISSN	15213765
Journal	Chemistry - A European Journal
Issue Number	46
Volume Number	21
Language	English
Publisher	Wiley-VCH;ChemPubSoc Europe
Publisher Date	2015-11-09
Publisher Place	Germany
Access Restriction	Open
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Catalysis

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