High-Valent Nonheme Iron-Oxo Complexes: Synthesis and Reactivity

这项化学合成（SYN）项目的研究奖支持明尼苏达大学的Lawrence Que教授合成高自旋铁(IV)-氧中间体的类似物，这些中间体是许多非血红素铁加氧酶的关键氧化剂。相比之下，迄今为止描述的绝大多数合成氧化铁（IV）配合物都是低自旋的，DFT计算预测其反应性要比高自旋的配合物低得多。为了验证DFT预测，Que教授和他的团队将合成具有高自旋Fe(IV)=O单位的配合物，并尽可能通过x射线晶体学和光谱方法的组合来表征它们，以便详细了解它们的几何和电子结构。高自旋配合物氧化底物C-H键的能力将与其性质相关，并与低自旋Fe=O配合物进行比较，以确定控制Fe=O反应性的因素。更好地了解这些因素对于开发更有效的C-H键氧化催化剂将是重要的。氧化过程在生物学和工业环境中都很重要。深入了解大自然如何有效地进行C-H键的氧化，对设计大规模化学氧化催化剂具有重要的影响，这些催化剂将更节能、更环保、更少浪费我们的资源。

This research award in the Chemical Synthesis (SYN) program supports work by Professor Lawrence Que of the University of Minnesota to generate synthetic analogs of high-spin iron(IV)-oxo intermediates that serve as the key oxidants for many nonheme iron oxygenases. In contrast, the vast majority of synthetic oxoiron(IV) complexes described to date are low-spin, which DFT calculations predict to be much less reactive than their high-spin counterparts. To test the DFT prediction, Professor Que and his team will synthesize complexes with high-spin Fe(IV)=O units and characterize them by X-ray crystallography whenever possible and by a combination of spectroscopic methods in order to gain detailed insight into their geometric and electronic structures. The abilities of the high-spin complexes to oxidize substrate C-H bonds will be correlated with their properties and compared to those of low-spin Fe=O complexes to determine what factors control Fe=O reactivity. A greater understanding of such factors will be important for the development of more effective C-H bond oxidation catalysts.Oxidation processes are important in biology and in industrial settings. Gaining insights into how Nature carries out the oxidation of C-H bonds efficiently has important ramifications in the design of oxidation catalysts for large scale chemistry that will be more energy efficient, more environmentally friendly, and less wasteful of our resources.