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首页> 外文期刊>Chemistry: A European journal >Cyclometallation and Hydrogen/Deuterium Exchange Reactions of anArylphosphine Ligand upon Coordination to {IrACHTUNGTRENUNG(h5-C5Me5)}
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Cyclometallation and Hydrogen/Deuterium Exchange Reactions of anArylphosphine Ligand upon Coordination to {IrACHTUNGTRENUNG(h5-C5Me5)}

机译：芳基膦配体与{IrACHTUNGTRENUNG（h5-C5Me5）}配位后的环金属化和氢/氘交换反应

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摘要

The cyclopentadienyl ligand has played a pivotal role in organometallic chemistry ever since the synthesis and structural characterization of ferrocene was achieved in the early 1950s.[1] Half-sandwich metallocenes of rhodium and especially iridium, particularly those that contain the C5Me5 ligand, have provided truly remarkable advances in the field of C-H bond activation. An early important milestone was the observation in 1982 by the groups of Bergman and Graham of the intermolecular addition of alkane C-H bonds to electron-rich [(h5-C5Me5)Ir(L)] centers.[2] A subsequent,also impressive, breakthrough in this field was thediscovery by Bergman and co-workers that the electron-deficientcationic IrIII species [(h5-C5Me5)Ir(Me)ACHTUNGTRENUNG(PMe3)-ACHTUNGTRENUNG(ClCH2Cl)]+, isolated as the [BAr4 F]- salt ([BAr4F]-=[BACHTUNGTRENUNG(3,5-C6H3ACHTUNGTRENUNG(CF3)2)4]-), effects the selective cleavage of the C-H bonds of alkanes and arenes under unusually mild conditions(for example, C6H6 at 30 8C and CH4 at 10 8C).[3]
机译：自从1950年代初实现二茂铁的合成和结构表征以来，环戊二烯基配体就在有机金属化学中发挥了关键作用。[1]铑，尤其是铱的半三明治金属茂，特别是那些含有C5Me5配体的茂金属，在C-H键活化领域取得了令人瞩目的进步。一个早期的重要里程碑是在1982年，Bergman和Graham组观察到链烷烃C-H键在分子间加成到富电子的[（h5-C5Me5）Ir（L）]中心。[2]此领域随后的又一个令人印象深刻的突破是，Bergman及其同事发现了缺电子的IrIII物种[（h5-C5Me5）Ir（Me）ACHTUNGTRENUNG（PMe3）-ACHTUNGTRENUNG（ClCH2Cl）] +， [BAr4 F]-盐（[BAr4F]-= [BACHTUNGTRENUNG（3,5-C6H3ACHTUNGTRENUNG（CF3）2）4]-），可在异常温和的条件下影响烷烃和芳烃CH键的选择性裂解（例如， [3]在30 8C时为C6H6，在10 8C时为CH4）。[3]

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