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

高价非血红素铁氧配合物：合成和反应性

• 批准号: 1361773
• 负责人: Lawrence Que
• 金额: $ 44.4万
• 依托单位: University of Minnesota-Twin Cities
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2014
• 资助国家: 美国
• 起止时间: 2014-07-01 至 2017-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1361773&HistoricalAwards=false
• 关键词: Valent; Nonheme; Iron; Oxo; Complexes

This research award from the Chemical Synthesis (SYN) program supports work by Professor Lawrence Que of the University of Minnesota to study iron facilitated oxidation processes that are important in biology and in industrial settings. Gaining insights into how Nature carries out the oxidation of strong C-H bonds efficiently plays an important role 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. Professor Que is working closely with many graduate students and postdoctoral associates from diverse backgrounds and preparing them to become the leaders among the next generation of chemists.The proposed research aims to generate synthetic analogs of high-spin (S = 2) iron(IV)-oxo intermediates that serve as the key oxidants for many nonheme iron oxygenases. The vast majority of synthetic oxoiron(IV) complexes described to date have intermediate spin (S = 1), which DFT calculations predict to be much less reactive than their high-spin counterparts. To test the DFT prediction, we 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.

化学合成(SYN)计划颁发的这项研究奖支持了明尼苏达大学的劳伦斯·奎教授研究铁促进的氧化过程的工作，这一过程在生物学和工业环境中非常重要。深入了解大自然如何有效地进行强C-H键的氧化，对于设计更节能、更环保、更少浪费资源的大规模化学氧化催化剂具有重要作用。QUE教授正在与来自不同背景的许多研究生和博士后同事密切合作，为他们成为下一代化学工作者的领导者做准备。这项拟议的研究旨在产生高自旋(S=2)铁(IV)-氧中间体的合成类似物，这些中间体是许多非血红素铁加氧酶的关键氧化剂。到目前为止，绝大多数合成的氧合铁(IV)配合物都具有中等自旋(S=1)，密度泛函计算预测其活性比它们的高自旋对应物低得多。为了验证DFT预测，我们将合成具有高自旋Fe(IV)=O单元的配合物，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，以获得对它们的几何和电子结构的详细了解。高自旋络合物氧化底物C-H键的能力将与它们的性质相关联，并与低自旋Fe=O络合物进行比较，以确定控制Fe=O反应活性的因素。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。

项目成果

Oxoiron(IV) Tetramethylcyclam Complexes with Axial Carboxylate Ligands: Effect of Tethering the Carboxylate on Reactivity

• DOI: 10.1021/acs.inorgchem.6b02659
• 发表时间: 2017-03-20
• 期刊: INORGANIC CHEMISTRY
• 影响因子: 4.6
• 作者: Bigelow, Jennifer O.;England, Jason;Que, Lawrence, Jr.
• 通讯作者: Que, Lawrence, Jr.