德国埃尔朗根-纽伦堡大学Meyer, Karsten研究团队报道了一种氮化铁(VII)配合物的合成与表征。相关研究成果发表在2024年1月30日出版的《自然—化学》。

高氧化态铁配合物在许多催化过程中作为活性中间体发挥着关键作用，因此是吸引人的研究课题。定义明确的模型配合物的结构和光谱研究通常提供这些中间体的证据。除了这些配合物获得的基本分子和电子结构见解外，它们的反应性还影响人们对小分子和键活化化学催化反应机制的理解。

该文中，研究人员报道了一种稳定的八面体Fe(VI)氮化物配合物，和一种通过单电子氧化制备的独特Fe(VII)物种的合成、结构和光谱表征。超氧化的氮化铁（VII）通过分子内胺化机制和配体交换重排为铁(V)酰亚胺，这在光谱和计算上得到了表征。这使得能够对罕见的高价复杂氧化还原对的单个分子系统，进行联合反应性和稳定性研究。量子化学计算补充了光谱参数，并为这些超氧化氮化物配合物的抗磁性 (S=0) d² Fe(VI)和真正的S＝1/2，d¹ Fe(VII)构型提供了证据。

附：英文原文

Title: The synthesis and characterization of an iron(VII) nitrido complex

Author: Keilwerth, Martin, Mao, Weiqing, Malischewski, Moritz, Jannuzzi, Sergio A. V., Breitwieser, Kevin, Heinemann, Frank W., Scheurer, Andreas, DeBeer, Serena, Munz, Dominik, Bill, Eckhard, Meyer, Karsten

Issue&Volume: 2024-01-30

Abstract: Complexes of iron in high oxidation states are captivating research subjects due to their pivotal role as active intermediates in numerous catalytic processes. Structural and spectroscopic studies of well-defined model complexes often provide evidence of these intermediates. In addition to the fundamental molecular and electronic structure insights gained by these complexes, their reactivity also affects our understanding of catalytic reaction mechanisms for small molecule and bond-activation chemistry. Here, we report the synthesis, structural and spectroscopic characterization of a stable, octahedral Fe(VI) nitrido complex and an authenticated, unique Fe(VII) species, prepared by one-electron oxidation. The super-oxidized Fe(VII) nitride rearranges to an Fe(V) imide through an intramolecular amination mechanism and ligand exchange, which is characterized spectroscopically and computationally. This enables combined reactivity and stability studies on a single molecular system of a rare high-valent complex redox pair. Quantum chemical calculations complement the spectroscopic parameters and provide evidence for a diamagnetic (S=0) d 2 Fe(VI) and a genuine S=1/2, d 1 Fe(VII) configuration of these super-oxidized nitrido complexes.

DOI: 10.1038/s41557-023-01418-4

Source: https://www.nature.com/articles/s41557-023-01418-4