首页> 外文期刊>Chemistry: A European journal >Adamantylidene Addition to M_3N@I_h-C_(80) (M=Sc, Lu) and Sc_3N@D_(5h)-C_(80): Synthesis and Crystallographic Characterization of the [5,6]-Open and [6,6]-Open Adducts
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Adamantylidene Addition to M_3N@I_h-C_(80) (M=Sc, Lu) and Sc_3N@D_(5h)-C_(80): Synthesis and Crystallographic Characterization of the [5,6]-Open and [6,6]-Open Adducts

机译:Adamantylidene添加到M_3N @ i_h-c_(80)(m = sc,lu)和sc_3n @ d_(5h)-c_(80):[5,6] -open和[6,6]的合成和晶体表征 -pen加合物

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摘要

Additions of adamantylidene (Ad) to M_3N@I_h-C_(80) (M=Sc, Lu) and Sc_3N@D_(5h)-C_(80) have been accomplished by photochemical reactions with 2-adamantyl-2,3’-[3H]-diazirine (1). In M_3N@I_h-C_(80), the addition led to rupture of the [6,6]- or [5,6]-bonds of the I_h-C_(80) cage, forming the [6,6]-open fulleroid as the major isomer and the [5,6]-open fulleroid as the minor isomer. In Sc_3N@D_(5h)-C_(80), the addition also proceeded regioselectively to yield three major isomeric Ad mono-adducts, despite the fact that there are nine types of C@C bonds in the D_(5h)-C_(80) cage. The molecular structures of the seven Ad mono-adducts, including the positions of the encaged trimetallic nitride clusters, have been unambiguously determined through single-crystal XRD analyses. Furthermore, results have shown that stepwise addition of Ad to Lu_3N@I_h-C_(80) affords several Ad bis-adducts, two of which have been isolated and characterized. The X-ray structure of one bis-adduct clearly revealed that the second Ad addition took place at a [6,6]-bond close to an endohedral metal atom. Theoretical calculations have also been performed to rationalize the regioselectivity.
机译:通过使用2-anamantyl-2,3'-的光化学反应,通过与2-anamantyl-2,3'-的光化学反应来完成将亚氨基乙烯(Ad)〜M_3N @ i_h-c_(80)(m = sc,lu)和sc_3n @ d_(50)进行了添加。 [3H] - 二嗪(1)。在M_3N @ I_H-C_(80)中,加法导致[6,6] - 或[5,6]箱的破裂,或者是i_h-c_(80)笼的,形成[6,6] -open富含重量异构体和[5,6] -open fulleroid作为未成年人。在SC_3N @ D_(5H)-C_(80)中,另外还进行了区域选择性,以产生三个主要的异构广告单体加合物,尽管D_(5h)-c_中有九种C键键( 80)笼子。通过单晶XRD分析分析,七种Ad单合物的分子结构包括所持式三族氮化物簇的位置,已经明确地确定。此外,结果表明,AD到Lu_3N @ i_H-C_(80)的逐步添加提供了几种AD双加合物,其中两个已被隔离和表征。一个双加合物的X射线结构清楚地表明,在靠近腹皮细胞原子的A [6,6] - 粘液中发生了第二种添加。也已经进行了理论计算以合理化区域选择性。

著录项

  • 来源
    《Chemistry: A European journal》 |2017年第27期|共10页
  • 作者单位

    Department of Chemistry Tokyo Gakugei University Tokyo 184–8501 (Japan);

    Life Science Center of Tsukuba Advanced Research Alliance University of Tsukuba Ibaraki 305–8577 (Japan);

    Life Science Center of Tsukuba Advanced Research Alliance University of Tsukuba Ibaraki 305–8577 (Japan);

    Life Science Center of Tsukuba Advanced Research Alliance University of Tsukuba Ibaraki 305–8577 (Japan);

    Life Science Center of Tsukuba Advanced Research Alliance University of Tsukuba Ibaraki 305–8577 (Japan);

    Life Science Center of Tsukuba Advanced Research Alliance University of Tsukuba Ibaraki 305–8577 (Japan);

    Life Science Center of Tsukuba Advanced Research Alliance University of Tsukuba Ibaraki 305–8577 (Japan);

    Department of Physical and Macromolecular Chemistry Charles University in Prague 128 43 Prague 2 (Czech Republic);

    Department of Chemistry Tokyo Gakugei University Tokyo 184–8501 (Japan);

    Department of Chemistry Tokyo Gakugei University Tokyo 184–8501 (Japan);

    Key Laboratory of Functional Inorganic Material Chemistry Ministry of Education School of Chemistry and Materials Science Heilongjiang University Harbin 150080 (P.R. China);

    State Key Laboratory of Materials Processing and Die and Mold Technology School of Materials Science and Engineering Huazhong University of Science and Technology Wuhan 430074 (P.R. China);

    Department of Chemistry University of California Davis California 95616 (USA);

    Department of Chemistry University of California Davis California 95616 (USA);

    Fukui Institute for Fundamental Chemistry Kyoto University Kyoto 606–8103 (Japan);

    Department of Chemistry Tokyo Gakugei University Tokyo 184–8501 (Japan);

  • 收录信息
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 应用化学;
  • 关键词

    cycloaddition; fullerenes; rare earths; regioselectivity; X-ray diffraction;

    机译:环加成;富勒烯;稀土;区域选择性;X射线衍射;

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