Facile H/D Exchange at (Hetero)Aromatic Hydrocarbons Catalyzed by a Stable Trans-Dihydride N-Heterocyclic Carbene (NHC) Iron Complex.
Facile H/D Exchange at (Hetero)Aromatic Hydrocarbons Catalyzed by a Stable Trans-Dihydride N-Heterocyclic Carbene (NHC) Iron Complex.
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DOI：
10.1021/jacs.0c07689
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发表时间：
2020-10-07
影响因子：
15
通讯作者：
Ruiter G
中科院分区：
文献类型：
--
作者：
Garhwal S;Kaushansky A;Fridman N;Shimon LJW;Ruiter G
在过去的十年中，地球丰富的金属钳配合物在均相催化中发挥了重要作用。然而，尽管进行了大量的研究工作，铁PCcarbeneP钳形配合物的合成迄今为止仍然难以捉摸。本文报道了第一个PCNHCP功能化铁配合物[（PCNHCP）FeCl 2]（1）的合成和相应的反式二氢化铁（II）二氮配合物[（PCNHCP）Fe（H）2N 2）]（2）的反应性。配合物2在N2气氛下是稳定的，并且在温和条件（50 °C，N2）下对于（杂）芳族烃的氢同位素交换是高度活性的。用苯-d 6作为氘源，容易还原的官能团如酯和酰胺是良好耐受的，有助于总体宽的底物范围（例如，卤化物、醚和胺）。密度泛函理论研究表明，C（sp2）-H键的活化是通过一个复合物辅助的σ-键复分解途径实现的，本文对此进行了进一步的讨论。
Earth-abundant metal pincer complexes have played an important role in homogeneous catalysis during the last ten years. Yet, despite intense research efforts, the synthesis of iron PCcarbeneP pincer complexes has so far remained elusive. Here we report the synthesis of the first PCNHCP functionalized iron complex [(PCNHCP)FeCl2] (1) and the reactivity of the corresponding trans-dihydride iron(II) dinitrogen complex [(PCNHCP)Fe(H)2N2)] (2). Complex 2 is stable under an atmosphere of N2 and is highly active for hydrogen isotope exchange at (hetero)aromatic hydrocarbons under mild conditions (50 °C, N2). With benzene-d6 as the deuterium source, easily reducible functional groups such as esters and amides are well tolerated, contributing to the overall wide substrate scope (e.g., halides, ethers, and amines). DFT studies suggest a complex assisted σ-bond metathesis pathway for C(sp2)–H bond activation, which is further discussed in this study.
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影响因子：
16.6
作者：
Eizawa A;Arashiba K;Tanaka H;Kuriyama S;Matsuo Y;Nakajima K;Yoshizawa K;Nishibayashi Y
通讯作者：
Nishibayashi Y
影响因子：
15
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通讯作者：
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影响因子：
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作者：
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通讯作者：
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影响因子：
2.8
作者：
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通讯作者：
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