Exploring the reaction mechanism of a cationic terminal iridium methylene complex with ethyl diazoacetate, a Lewis base and dihydrogen: a quantum chemistry study
Exploring the reaction mechanism of a cationic terminal iridium methylene complex with ethyl diazoacetate, a Lewis base and dihydrogen: a quantum chemistry study
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DOI：
10.1039/c4nj00757c
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发表时间：
2014-08
影响因子：
3.3
通讯作者：
Xincheng Ye;Liu Yang;Zunyi Wu;Gerui Ren;Yanbin Lu;Tingting Sun;Qun-fang Lei;Wenjun Fang;Hujun Xie
中科院分区：
文献类型：
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作者：
Xincheng Ye;Liu Yang;Zunyi Wu;Gerui Ren;Yanbin Lu;Tingting Sun;Qun-fang Lei;Wenjun Fang;Hujun Xie
用密度泛函理论（DFT）研究了中性甲基配合物[（PONOP）Ir（CH 3）]通过α-氢化物夺取形成阳离子亚甲基配合物[（PONOP）Ir（CH 2）]+（PONOP = 2，6-双（二叔丁基膦基）吡啶）的机理及其与重氮乙酸乙酯、刘易斯碱（PMe 3）和二氢的反应性.计算结果表明，重氮乙酸乙酯与亚甲基配体通过直接的C-C偶联反应生成η2-烯烃配合物.一个叶立德化合物给出了这种阳离子亚甲基配合物与PMe 3的反应。此外，该阳离子亚甲基络合物的IrCH 2部分的氢解导致氢化物铱络合物。我们的计算可以提供新的见解亚甲基配合物的反应性。
The mechanisms for the formation of a cationic methylene complex [(PONOP)Ir(CH2)]+ (PONOP = 2,6-bis(di-tert-butylphosphinito)pyridine) via α-hydride abstraction from a neutral methyl complex [(PONOP)Ir(CH3)] and its reactivity with ethyl diazoacetate, a Lewis base (PMe3) and dihydrogen have been studied computationally with the aid of density functional theory (DFT). The calculation results show that the η2-alkene complex can be formed via a direct C–C coupling reaction involving the methylene ligand and ethyl diazoacetate. A ylide compound is given for the reaction of this cationic methylene complex with PMe3. In addition, hydrogenolysis of the IrCH2 moiety of this cationic methylene complex results in a hydride iridium complex. Our calculations could provide new insights into the reactivity of methylene complexes.