Fe-mediated C-O cleavage and C-C bond forming reactions from CO2 and CO substrates

Fe 介导的 CO2 和 CO 底物的 C-O 裂解和 C-C 键形成反应

• 批准号: 0750234
• 负责人: Jonas Peters
• 金额: $ 37万
• 依托单位: Massachusetts Institute of Technology
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2008
• 资助国家: 美国
• 起止时间: 2008-04-15 至 2010-10-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0750234&HistoricalAwards=false
• 关键词: Fe; mediated; cleavage; bond; forming

This award by the Inorganic, Bioinorganic, and Organometallic Chemistry Program supports the work of Professor Jonas Peters at the Massachusetts Institute of Technology to investigate (phosphinoborate)iron(I) compounds that are structurally unusual by virtue of their relatively low coordination numbers and geometry. These complexes feature iron-nitrogen multiple bonds. These complexes have been found to mediate C-O cleavage pathways that effect partial or complete CO extrusion or reductive C-C coupling to produce oxalate. The synthesis of monometallic and bimetallic iron(oxo) species will also be explored particularly in terms of dihydrogen activation. Finally, the ability to activate carbon dioxide and release iron carbonyl products opens the door to using carbon dioxide as a synthon for C-C coupling reactions that exploit CO as a carbene or carbyne precursor. The synthesis and reactivities of iron(carbenes) and (carbynes) with hydrogen will also be investigated. In addition to the reductive degradation of carbon dioxide which may have important ramifications for the reduction of greenhouse gases and the development of new methods of carbon management, this research will encourage undergraduate and graduate students to become sensitive to energy conversion issues as they enter their chemical careers.

该奖项由无机、生物无机和有机金属化学项目颁发，支持麻省理工学院乔纳斯·彼得斯教授的工作，以研究（膦硼酸）铁（I）化合物，这些化合物因其相对较低的配位数和几何形状而在结构上不寻常。 这些配合物具有铁-氮多重键。 已发现这些复合物介导 C-O 裂解途径，从而影响部分或完全 CO 挤出或还原性 C-C 偶联以产生草酸盐。 还将探索单金属和双金属铁（氧）物质的合成，特别是在氢气活化方面。 最后，活化二氧化碳并释放羰基铁产物的能力为使用二氧化碳作为C-C偶联反应的合成子打开了大门，该反应利用CO作为卡宾或卡炔前体。 还将研究铁（卡宾）和（卡宾）与氢的合成和反应性。除了二氧化碳的还原降解可能对减少温室气体和开发碳管理新方法产生重要影响外，这项研究还将鼓励本科生和研究生在进入化学领域时对能量转换问题变得敏感职业生涯。