First Introduction of an Azulenyl Group into the Bismuth and Antimony Center. Synthesis and Structure of Azulenylbismuthanes and Their Difluorides
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- 作者：A. F. M. Mustafizur Rahman ; Toshihiro Murafuji ; Kei Kurotobi ; Yoshikazu Sugihara ; and Nagao Azuma
- 刊名：Organometallics
- 出版年：2004
- 出版时间：December 20, 2004
- 年：2004
- 卷：23
- 期：26
- 页码：6176 - 6183
- 全文大小：207K
- 年卷期：v.23,no.26(December 20, 2004)
- ISSN：1520-6041
文摘
A nonalternant organyl ligand derived from azulene, a 1,3-dichloro-2-azulenyl group, isintroduced for the first time into the bismuth and antimony center. Conversion of theazulenylbismuthanes into the pentacoordinated difluorides by xenon difluoride promotesthe 
-polarization of the azulene nucleus, which is detected as a color change in solution aswell as changes in the chemical shifts of the 13C NMR spectra. A similar tendency is observedin the antimony congeners. The X-ray crystallographic study of (1,3-dichloro-2-azulenyl)diphenylbismuth difluoride (20b) reveals that intermolecular - stacking takes placebetween the azulenyl groups through the interaction of the five-membered ring with theseven-membered ring. This may reflect the more polarized azulenyl group of the difluorides,which strengthens the stacking interaction.
-polarization of the azulene nucleus, which is detected as a color change in solution aswell as changes in the chemical shifts of the 13C NMR spectra. A similar tendency is observedin the antimony congeners. The X-ray crystallographic study of (1,3-dichloro-2-azulenyl)diphenylbismuth difluoride (20b) reveals that intermolecular - stacking takes placebetween the azulenyl groups through the interaction of the five-membered ring with theseven-membered ring. This may reflect the more polarized azulenyl group of the difluorides,which strengthens the stacking interaction.