Is C60 buckminsterfullerene aromatic?

被引:57
|
作者
Chen, Zhongfang [1 ]
Wu, Judy I. [2 ]
Corminboeuf, Clemence [3 ]
Bohmann, Jonathan [4 ]
Lu, Xin [5 ,6 ]
Hirsch, Andreas [7 ]
Schleyer, Paul von Rague [2 ]
机构
[1] Univ Puerto Rico, Dept Chem, San Juan, PR 00931 USA
[2] Univ Georgia, Dept Chem, Ctr Computat Chem, Athens, GA 30602 USA
[3] Ecole Polytech Fed Lausanne, Dept Chem, Lausanne, Switzerland
[4] SW Res Inst, Synth & Drug Delivery Grp, San Antonio, TX 78238 USA
[5] Xiamen Univ, State Key Lab Phys Chem Solid Surfaces, Xiamen 361005, Peoples R China
[6] Xiamen Univ, Dept Chem, Coll Chem & Chem Engn, Xiamen 361005, Peoples R China
[7] Univ Erlangen Nurnberg, Inst Organ Chem LS 2, D-91054 Erlangen, Germany
基金
美国国家科学基金会;
关键词
INDEPENDENT CHEMICAL-SHIFTS; SPHERICAL AROMATICITY; ICOSAHEDRAL C-60; RING CURRENTS; MAGNETIC-SUSCEPTIBILITY; HE-3; NMR; FULLERENES; STABILIZATION; MOLECULE; DELOCALIZATION;
D O I
10.1039/c2cp42146a
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
C-60 does not have "superaromatic'' or even aromatic character, but is a spherically pi antiaromatic and enormously strained species. This explains its very large and positive heat of formation (610 +/- 30 kcal mol(-1)). The pi electron character of C-60 was analyzed by dissected nucleus independent chemical shifts (NICS). The results were employed to examine the scope and limitations of Hirsch's 2(N + 1)(2) spherical aromaticity rule for several globular cages. C-20(2+) (18 pi electrons) and C-60(10+) (50 pi electrons) are spherically pi aromatic, but C-20 (20 pi electrons) and C-60 (60 pi electrons) are spherically pi antiaromatic, due to the high paratropicity of their half-filled pi subshells. Limitations for Hirsch's rule, for clusters with more than 50 pi electrons, are illustrated by e.g. the pi aromaticity of the 66 pi electron C-60(6-) and the lack of pi aromaticity of the 72 pi electron C48N12 and C-60(12-)
引用
收藏
页码:14886 / 14891
页数:6
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