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Thermally Stable Redox Noninnocent Bathocuproine-Iron Complex for Cycloaddition Reactions
ACS Catalysis ( IF 11.3 ) Pub Date : 2023-03-27 , DOI: 10.1021/acscatal.3c00353
Mae Féo 1 , Nikki J. Bakas 2 , Aleksa Radović 2 , William Parisot 1 , Anne Clisson 1 , Lise-Marie Chamoreau 3 , Mansour Haddad 1 , Virginie Ratovelomanana-Vidal 1 , Michael L. Neidig 2, 4 , Guillaume Lefèvre 1
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In this work, we aim to formally design iron(0) complexes combined with a phenanthroline-type ligand (phen) and investigate their utility in cycloaddition catalysis. Owing to the strong noninnocence of the phen scaffold, its ligation to reduced iron oxidation states classically affords particularly unstable species. The reported examples of such well-defined coordination complexes are thus particularly scarce. We demonstrate herein that a strategic steric protection of the C4 and C7 positions of the phen ring leads to neutral (N,N)2Fe species, which exhibits an unprecedented thermal and kinetic stability, amenable to its easy use as an in situ generated precursor in catalytic processes. The electronic structure of this noninnocent complex has been fully rationalized, and its promising catalytic activity in alkyne [2 + 2 + 2] cyclizations is discussed. Given its intrinsic thermal stability due to the noninnocent behavior of the (N,N) ligand, (N,N)2Fe appears to be an efficient dormant state of the catalytic process, precluding deactivation of iron as nonreactive aggregates.

中文翻译:

用于环加成反应的热稳定氧化还原非无辜浴铜灵-铁络合物

在这项工作中,我们旨在正式设计与菲咯啉型配体 (phen) 结合的铁 (0) 配合物,并研究它们在环加成催化中的效用。由于 phen 支架的强非纯真性,它与还原铁氧化态的连接通常会提供特别不稳定的物种。因此,此类定义明确的配位复合物的报道实例特别稀少。我们在此证明,phen 环的 C4 和 C7 位置的战略空间保护导致中性 (N,N) 2 Fe 物种,它表现出前所未有的热稳定性和动力学稳定性,易于用作原位催化过程中产生的前体。这种非无辜配合物的电子结构已完全合理化,并讨论了其在炔烃 [2 + 2 + 2] 环化中有前途的催化活性。由于 (N,N) 配体的非无害行为,鉴于其固有的热稳定性,(N,N) 2 Fe 似乎是催化过程的有效休眠状态,排除了铁作为非反应性聚集体的失活。
更新日期:2023-03-27
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