School of Chemistry, University College Dublin, D04 V1W8 Belfield, Dublin 4, Ireland.
Molecules. 2020 Oct 15;25(20):4730. doi: 10.3390/molecules25204730.
The intermediacy of short-lived isoindenes, generated in the course of metallotropic or silatropic shifts over the indene skeleton, can be shown by Diels-Alder trapping with tetracyanoethylene, leading to the complete elucidation of the dynamic behaviour of a series of polyindenylsilanes. Cyclopentadienones, bearing ferrocenyl and multiple phenyl or naphthyl substituents undergo [4 + 2] cycloadditions with diaryl acetylenes or triphenylcyclopropene to form the corresponding polyarylbenzenes or cycloheptatrienes. The heptaphenyltropylium cation, [CPh], was shown to adopt a nonplanar shallow boat conformation. In contrast, the attempted Diels-Alder reaction of tetracyclone and phenethynylfluorene yielded electroluminescent tetracenes. Finally, benzyne addition to 9-(2-indenyl)anthracene, and subsequent incorporation of a range of organometallic fragments, led to development of an organometallic molecular brake.
在茚骨架上的金属型或硅型迁移过程中生成的短寿命异茚，可以通过与四氰乙烯的 Diels-Alder 捕获来证明，从而彻底阐明一系列聚茚基硅烷的动态行为。带有二茂铁基和多个苯基或萘基取代基的环戊二烯酮与二芳基乙炔或三苯基环丙烯发生[4+2]环加成反应，形成相应的多芳基苯或环庚三烯。证明了七苯基三亚甲基翁阳离子[CPh] 采用非平面浅船构象。相比之下，尝试用四环酮和苯乙炔基芴进行 Diels-Alder 反应得到了电致发光的四环。最后，苯炔加成到 9-(2-茚基)蒽上，并随后引入一系列有机金属片段，导致开发了一种有机金属分子制动器。
