Curve-Structured Phenalenyl Chemistry: Synthesis, Electronic Structure, and Bowl-Inversion Barrier of a Phenalenyl-Fused Corannulene Anion

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• 作者：Shinsuke Nishida ; Yasushi Morita ; Akira Ueda ; Tadahiro Kobayashi ; Kozo Fukui ; Kanako Ogasawara ; Kazunobu Sato ; Takeji Takui ; Kazuhiro Nakasuji
• 刊名：Journal of the American Chemical Society
• 出版年：2008
• 出版时间：November 12, 2008
• 年：2008
• 卷：130
• 期：45
• 页码：14954-14955
• 全文大小：140K
• 年卷期：v.130,no.45(November 12, 2008)
• ISSN：1520-5126

文摘

We have demonstrated the features of curve-structured phenalenyl chemistry, for the first time. A phenalenyl-fused corannulene anion has been designed by the annelation of a six-memberd ring across peri-positions of corannulene and generated as a stable species in a degassed solution. The ¹H and ¹³C NMR spectra have shown the highly symmetrical structure and high-field shifts of protons and carbons at the asterisked positions in the chemical structure, indicating the occurrence of large negative charge densities at these positions. These results well agree with the HOMO picture and the electrostatic potential surface, demonstrating the phenalenyl anion-type electronic structure is retained in the curved-surface π-system. The calculated bowl-inversion barrier of the anion (11.3 kcal/mol) is larger than that of corannulene (9.2 kcal/mol) because of peri-annelation of the corannulene skeleton. The calculations of the barriers of the neutral radical (12.6 kcal/mol), radical dianion (8.1 kcal/mol), and trianion (5.4 kcal/mol) of the phenalenyl-fused corannulene have exhibited a stepwise flattening of the curvature with increase in negative charge. Therefore, we have revealed that the bowl-inversion barrier of the anion is governed by the setoff of the peri-annelation and negative charge effects.