Mechanistic Studies on Iron-Catalyzed Dehydrogenation of Amines Involving Cyclopentadienone Iron Complexes─Evidence for Stepwise Hydride and Proton Transfer,ACS Catalysis

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Mechanistic Studies on Iron-Catalyzed Dehydrogenation of Amines Involving Cyclopentadienone Iron Complexes─Evidence for Stepwise Hydride and Proton Transfer
ACS Catalysis ( IF 11.3 ) Pub Date : 2023-06-12 , DOI: 10.1021/acscatal.3c01779
Srimanta Manna ₁ , Joannes Peters ₁ , Aitor Bermejo-López ₁ , Fahmi Himo ₁ , Jan-E. Bäckvall ₁

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The mechanism of dehydrogenation of amines catalyzed by (cyclopentadienone)iron carbonyl complexes was studied by means of kinetic isotope effect (KIE) measurements, intermediate isolation, and density functional theory calculations. The (cyclopentadienone)iron–amine intermediates were isolated and characterized by ¹H and ¹³C NMR spectroscopy as well as X-ray crystallography. The isolated iron–amine complexes are quite stable and undergo a formal β-hydride elimination to produce imine and iron hydride complexes. The KIEs observed for the iron-catalyzed dehydrogenation of 4-methoxy-N-(4-methylbenzyl)aniline are in accordance with stepwise dehydrogenation. The density functional calculations corroborate a stepwise mechanism involving a rate-determining hydride transfer from amine to iron to yield a metal hydride and an iminium intermediate, followed by a proton transfer from the iminium ion to the oxygen of the cyclopentadienone ligand.

中文翻译：

涉及环戊二烯酮铁络合物的铁催化胺脱氢的机理研究─逐步氢化物和质子转移的证据

通过动力学同位素效应(KIE)测量、中间体分离和密度泛函理论计算研究了(环戊二烯酮)铁羰基配合物催化胺脱氢的机理。(环戊二烯酮)铁胺中间体被分离并通过¹ H 和¹³ C NMR 光谱以及 X 射线晶体学进行表征。分离的铁胺络合物非常稳定，并经过正式的β-氢化物消除，产生亚胺和氢化铁络合物。观察到的铁催化 4-甲氧基-N脱氢的 KIE-(4-甲基苄基)苯胺按照分步脱氢制得。密度泛函计算证实了一种逐步机制，涉及从胺到铁的决定速率的氢化物转移，产生金属氢化物和亚胺中间体，然后是质子从亚胺离子转移到环戊二烯酮配体的氧。

更新日期：2023-06-12

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