化学
区域选择性
铱
金属环
位阻效应
插入反应
戒指(化学)
金属
立体化学
选择性
碳氢化合物
药物化学
催化作用
有机化学
X射线晶体学
物理
光学
衍射
作者
Martin Jakoobi,Yancong Tian,Roman Boulatov,Alexey G. Sergeev
摘要
Regioselective metal insertion into aromatic C–C bonds is a long-standing problem critical for development of new arene functionalizations and cleaner conversion of fossil fuel into value-added chemicals. We report reversible insertion of iridium into the aromatic C–C bonds of η4-bound methyl arenes to give eight-membered diiridium metallacycles with yields up to 99%. While at 50–100 °C the reaction yields a mixture of isomers corresponding to iridium insertion in both unsubstituted and Me-substituted ring C–C bonds, at 150 °C a single isomer dominates. Kinetic and DFT studies suggest that at 150 °C insertion of iridium is reversible, allowing equilibration of the metallacycle products via a diiridium arene sandwich complex. The selectivity of metal insertion is determined by the relative stabilities of isomeric metallacycles governed by steric repulsion between methyl groups of the hydrocarbon chain of the cleaved arene and the Cp* ligands.
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