Suzuki Noriyuki, Ban Sayaka, Mochizuki Ayari, Ito Saki
Department of Materials and Life Sciences, Faculty of Science and Technology, Sophia University, 7-1 Kioi-cho, Chiyoda-ku, Tokyo 102-8554, Japan.
Dalton Trans. 2021 Nov 16;50(44):16265-16272. doi: 10.1039/d1dt03313a.
Reactions of five-membered zirconacycloalkynes and zirconacyloallenes (1-zirconacyclopent-3-ynes and 1-zirconacyclopenta-2,3-dienes) with an excess of CpZr(H)Cl, known as the Schwartz reagent, were studied. Both reactions gave five-membered zirconacycloalkenes, 1-zirconacyclopent-3-enes without subsequent work-up such as protonolysis and hydrogenolysis. The product was identical to the zirconocene-diene complex that was prepared from CpZr(-Bu) (Negishi reagent) and the corresponding 1,4-disubstituted 1,3-dienes. These results indicate that formal hydrogenation by metal hydride took place. The use of diisobutylaluminum hydride or 9-borabicyclo[3.3.1]nonane also gave the same product, albeit in lower yields. The reactions starting from deuterated compounds suggested that double hydrozirconation followed by elimination of a dinuclear zirconium complex resulted in the hydrogenated products.
研究了五元锆杂环炔烃和锆杂环丙二烯（1-锆杂环戊-3-炔烃和1-锆杂环戊-2,3-二烯）与过量的CpZr(H)Cl（即施瓦茨试剂）的反应。这两种反应均生成了五元锆杂环烯烃，即1-锆杂环戊-3-烯，无需后续诸如质子解和氢解等后处理操作。该产物与由CpZr(-Bu)（根岸试剂）和相应的1,4-二取代1,3-二烯制备的二茂锆-二烯配合物相同。这些结果表明发生了金属氢化物的形式氢化反应。使用二异丁基氢化铝或9-硼双环[3.3.1]壬烷也能得到相同的产物，尽管产率较低。从氘代化合物开始的反应表明，双锆氢化反应随后消除双核锆配合物导致了氢化产物的生成。
