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

化学合成（SYN）计划的这项研究奖支持明尼苏达大学的Lawrence Que教授的工作，以生成高自旋铁（IV）-氧代中间体的合成类似物，这些中间体作为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合铁（IV）络合物是低自旋的，DFT计算预测其反应性比它们的高自旋对应物低得多。 为了测试DFT预测，Que教授和他的团队将合成具有高自旋Fe（IV）=O单元的复合物，并尽可能通过X射线晶体学和光谱方法的组合对其进行表征，以详细了解其几何和电子结构。 高自旋络合物氧化衬底C-H键的能力将与它们的性质相关，并与低自旋Fe=O络合物的性质进行比较，以确定哪些因素控制Fe=O反应性。 更好地理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是重要的。 深入了解大自然如何有效地进行C-H键的氧化，对于设计用于大规模化学的氧化催化剂具有重要的影响，这些催化剂将更加节能，更加环保，并且减少对我们资源的浪费。

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.