在一个Cp*Ir(III)配合物中，亚乙烯基重排与碳二取代内炔的1,2-插入之间的竞争。
Competition between vinylidene rearrangement and 1,2-insertion of carbon-disubstituted internal alkynes at a Cp*Ir(III) complex.
作者信息
Ikeda Yousuke, Kodama Shintaro, Tsuchida Noriko, Ishii Youichi
机构信息
Department of Applied Chemistry, Faculty of Science and Engineering, Chuo University, 1-13-27 Kasuga, Bunkyo-ku, Tokyo, Japan.
出版信息
Dalton Trans. 2015 Oct 28;44(40):17448-52. doi: 10.1039/c5dt02207j. Epub 2015 Sep 2.
Competition between vinylidene rearrangement/1,1-insertion and 1,2-alkyne insertion into the Ir-Ar bond of Cp*Ir(ppy-F4) was observed on reaction with diarylacetylenes. The former process afforded the iridacycle 2via the subsequent 1,4-Ir migration, whereas the latter led to the pyridoisoquinolinium complex 4. Detailed analysis revealed that 4 isomerizes to 2 by heating at 50 °C.
在与二芳基乙炔反应时，观察到[Cp*Ir(ppy-F4)]⁺的亚乙烯基重排/1,1-插入与1,2-炔烃插入Ir-Ar键之间的竞争。前一过程通过随后的1,4-Ir迁移得到铱杂环2，而后一过程则生成吡啶并异喹啉鎓配合物4。详细分析表明，4在50℃加热时异构化为2。
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