氮硼杂双环壬二烯经光致和热致可逆异构化生成氮硼杂苯并降蒈烯。
Reversible photochemical and thermal isomerization of azaboratabisnorcaradiene to azaborabenzotropilidene.
机构信息
Department of Chemistry, Queen's University, 90 Bader Lane, Kingston, Ontario (Canada).
出版信息
Angew Chem Int Ed Engl. 2014 Aug 18;53(34):9086-9. doi: 10.1002/anie.201404435. Epub 2014 Jun 18.
Two new tricyclic 1,2-azaboratabisnorcaradiene molecules (1 b and 2 b) generated through the photoisomerization of N-methyl-2-phenylimidazolyl-chelated dimesitylboranes (1 a and 2 a) have been found to undergo unusual photoisomerization, producing the first examples of 1,2-azaborabenzotropilidenes (1 c and 2 c), accompanied by a distinct color change, upon irradiation at 350 nm. Compounds 1 c and 2 c contain a conjugated alkylideneborane unit and can be fully reverted back to 1 b and 2 b, and subsequently to 1 a and 2 a upon heating. The mechanistic pathway of the new isomerism has been established to involve "walk" rearrangements by DFT computational studies.
通过 N-甲基-2-苯基咪唑基螯合二甲基硼烷（1a 和 2a）的光异构化生成了两个新的三环 1,2-氮杂硼二萘烷分子（1b 和 2b），发现它们会发生异常的光异构化，在 350nm 照射下产生了 1,2-氮杂苯并茚满（1c 和 2c）的首例实例，同时伴有明显的颜色变化。化合物 1c 和 2c 含有共轭的亚烷基硼烷单元，并且可以完全恢复为 1b 和 2b，然后在加热时恢复为 1a 和 2a。通过 DFT 计算研究，建立了新的异构化的机理途径，涉及“行走”重排。
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