CHEMISTRY OF THE HIGHER FULLERENES - PREPARATIVE ISOLATION OF C-76 BY HPLC AND SYNTHESIS, SEPARATION, AND CHARACTERIZATION OF DIELS-ALDER MONOADDUCTS OF C-70 AND C-76

被引:108
作者
HERRMANN, A
DIEDERICH, F
THILGEN, C
TERMEER, HU
MULLER, WH
机构
[1] ETH ZENTRUM,ORGAN CHEM LAB,CH-8092 ZURICH,SWITZERLAND
[2] HOECHST AG,ANGEW PHYS,D-65926 FRANKFURT,GERMANY
关键词
D O I
10.1002/hlca.19940770703
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
HPLC Separation of higher fullerenes was compared on two different stationary phases, and the preparative isolation of pure C-76 is described. Higher-fullerene derivatives 1 and 2 were prepared by Diels-Aldel reaction of C-70 and C-76 With an ortho-quinodimethane intermediate generated in situ. Three out of four possible isomeric C-70 monoadducts, i.e. 1a-e, and, for the first time, one isomeric C-76 monoadduct, i.e. 2c, could be isolated in pure form and characterized by H-1-NMR, C-13-HMR, UV/VIS, and mass spectrometry. Five other C-76 isomers i.e., 2a, b,d-f were obtained in partially separated product fractions. Coalescence temperatures and energy barriers were determined for the cyclohexene-ring inversion in two of the isomeric C-70 derivatives. The structure of the C-70 adducts could be deduced unambiguously From symmetry considerations based on high- and low-temperature H-1-NMR spectroscopy. A simple model for the qualitative evaluation of the local curvature of fullerene surfaces is presented and used for the prediction of addition sites in higher fullerenes. These predictions are compared to the experimental results mentioned above as well as to predictions resulting from pi-bond-order considerations and from calculated pyramidalization angles.
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收藏
页码:1689 / 1706
页数:18
相关论文
共 65 条
  • [51] REACTIONS OF C-60 AND C-70 WITH CYCLOPENTADIENE
    PANG, LSK
    WILSON, MA
    [J]. JOURNAL OF PHYSICAL CHEMISTRY, 1993, 97 (26) : 6761 - 6763
  • [52] SYNTHESIS AND X-RAY STRUCTURE OF A DIELS-ALDER ADDUCT OF C-60
    RUBIN, Y
    KHAN, S
    FREEDBERG, DI
    YERETZIAN, C
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993, 115 (01) : 344 - 345
  • [53] Sandstrom J., 1982, DYNAMIC NMR SPECTROS
  • [54] PURIFICATION OF GRAM QUANTITIES OF C-60 - A NEW INEXPENSIVE AND FACILE METHOD
    SCRIVENS, WA
    BEDWORTH, PV
    TOUR, JM
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (20) : 7917 - 7919
  • [55] ISOLATION AND SPECTROSCOPIC PROPERTIES OF SC2-AT-C74, SC2-AT-C82, AND SC2-AT-C84
    SHINOHARA, H
    YAMAGUCHI, H
    HAYASHI, N
    SATO, H
    OHKOHCHI, M
    ANDO, Y
    SAITO, Y
    [J]. JOURNAL OF PHYSICAL CHEMISTRY, 1993, 97 (17) : 4259 - 4261
  • [56] SMITH AB, 1993, AUG AM CHEM SOC M CH
  • [57] C-60, C-70, C-76, C-78 AND C-84 - NUMBERING, PI-BOND ORDER CALCULATIONS AND ADDITION PATTERN CONSIDERATIONS
    TAYLOR, R
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1993, (05): : 813 - 824
  • [58] C-13 NMR-SPECTROSCOPY OF C-76, C-78, C-84 AND MIXTURES OF C-86-C102 - ANOMALOUS CHROMATOGRAPHIC BEHAVIOR OF C-82, AND EVIDENCE FOR C70H12
    TAYLOR, R
    LANGLEY, GJ
    AVENT, AG
    DENNIS, TJS
    KROTO, HW
    WALTON, DRM
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1993, (06): : 1029 - 1036
  • [59] ISOLATION, SEPARATION AND CHARACTERIZATION OF THE FULLERENES C-60 AND C-70 - THE 3RD FORM OF CARBON
    TAYLOR, R
    HARE, JP
    ABDULSADA, AK
    KROTO, HW
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1990, (20) : 1423 - 1424
  • [60] THE CHEMISTRY OF FULLERENES
    TAYLOR, R
    WALTON, DRM
    [J]. NATURE, 1993, 363 (6431) : 685 - 693