title: Adamantylidene Addition to M3N@Ih-C80(M=Sc, Lu) and Sc3N@D5h-C80: Synthesis and Crystallographic Characterization of the [5,6]-Open and [6,6]-Open Adducts.
abstract: Additions of adamantylidene (Ad) to M3N@Ih-C80(M=Sc, Lu) and Sc3N@D5h-C80have been accomplished by photochemical reactions with 2-adamantyl-2,3'-[3H]-diazirine (1). In M3N@Ih-C80, the addition led to rupture of the [6,6]- or [5,6]-bonds of the Ih-C80cage, forming the [6,6]-open fulleroid as the major isomer and the [5,6]-open fulleroid as the minor isomer. In Sc3N@D5h-C80, 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 D5h-C80cage. 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 Lu3N@Ih-C80affords 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.
authors.affiliation: Department of Chemistry, Tokyo Gakugei University, Tokyo, 184-8501, Japan.
authors.forename: Michio
authors.initials: M
authors.lastname: Yamada
authors.affiliation: Life Science Center of Tsukuba Advanced Research Alliance, University of Tsukuba, Ibaraki, 305-8577, Japan.
authors.forename: Tsuneyuki
authors.initials: T
authors.lastname: Abe
authors.affiliation: Life Science Center of Tsukuba Advanced Research Alliance, University of Tsukuba, Ibaraki, 305-8577, Japan.
authors.forename: Chiharu
authors.initials: C
authors.lastname: Saito
authors.affiliation: Life Science Center of Tsukuba Advanced Research Alliance, University of Tsukuba, Ibaraki, 305-8577, Japan.
authors.forename: Toshiki
authors.initials: T
authors.lastname: Yamazaki
authors.affiliation: Life Science Center of Tsukuba Advanced Research Alliance, University of Tsukuba, Ibaraki, 305-8577, Japan.
authors.forename: Satoru
authors.initials: S
authors.lastname: Sato
authors.affiliation: Life Science Center of Tsukuba Advanced Research Alliance, University of Tsukuba, Ibaraki, 305-8577, Japan.
authors.forename: Naomi
authors.initials: N
authors.lastname: Mizorogi
authors.affiliation: Life Science Center of Tsukuba Advanced Research Alliance, University of Tsukuba, Ibaraki, 305-8577, Japan.|Department of Chemistry and Biochemistry, National Chung-Cheng University, Chia-Yi, 62117, Taiwan R.O.C.
authors.forename: Zdenek
authors.initials: Z
authors.lastname: Slanina
authors.affiliation: Department of Physical and Macromolecular Chemistry, Charles University in Prague, 128 43, Prague 2, Czech Republic.
authors.forename: Filip
authors.initials: F
authors.lastname: Uhlík
authors.affiliation: Department of Chemistry, Tokyo Gakugei University, Tokyo, 184-8501, Japan.|Department of Chemistry, Faculty of Science, Josai University, Saitama, 350-0295, Japan.
authors.forename: Mitsuaki
authors.initials: M
authors.lastname: Suzuki
authors.affiliation: Department of Chemistry, Tokyo Gakugei University, Tokyo, 184-8501, Japan.
authors.forename: Yutaka
authors.initials: Y
authors.lastname: Maeda
authors.affiliation: Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education, School of Chemistry and Materials Science, Heilongjiang University, Harbin, 150080, P.R. China.
authors.forename: Yongfu
authors.initials: Y
authors.lastname: Lian
authors.affiliation: 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.
authors.forename: Xing
authors.initials: X
authors.lastname: Lu
authors.affiliation: Department of Chemistry, University of California, Davis, California, 95616, USA.
authors.forename: Marilyn M
authors.initials: MM
authors.lastname: Olmstead
authors.affiliation: Department of Chemistry, University of California, Davis, California, 95616, USA.
authors.forename: Alan L
authors.initials: AL
authors.lastname: Balch
authors.affiliation: Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto, 606-8103, Japan.
authors.forename: Shigeru
authors.initials: S
authors.lastname: Nagase
authors.affiliation: 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.|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.|Foundation for Advancement of International Science, Ibaraki, 305-0821, Japan.
authors.forename: Takeshi
authors.initials: T
authors.lastname: Akasaka
keywords: X-ray diffraction; cycloaddition; fullerenes; rare earths; regioselectivity