Expanding Reductive Chemistry with the f Orbital Metals

NSF化学部化学合成（SYN）计划的这一奖项支持了加州大学欧文分校的William J. Evans教授利用镧系和锕系金属的独特性质进行氧化还原反应的基础研究。 这些还原/氧化反应构成了两种最基本的化学反应类型之一，并以无数方式影响着我们的生活。 由于镧系元素和锕系元素代表了元素周期表中的极端，它们提供了一组极好的金属，用于扩展氧化还原反应性的极限。 将研究像二氮和一氧化氮这样的小分子的活化，因为这些分子的氧化还原化学对于制造为世界提供食物的肥料至关重要，一氧化氮氧化还原化学对于理解烟雾和血管舒张等不同主题也至关重要。 该项目将探索获得金属的“虚拟”氧化态的方法，这些氧化态提供氧化还原反应性，即使它们从未被分离出来。 与金属连接的配体也将用于产生氧化还原反应性并开发可以影响多电子氧化还原过程的分子。 后者对于太阳能水分解等反应至关重要，这些反应有可能提供清洁能源，而不会增加大气中的二氧化碳水平。氧化还原化学的普遍性质意味着这项研究可以对科学和技术产生广泛的影响。 与此同时，学生将接受镧系金属化学和锕系金属化学的培训，镧系金属是一种具有众多技术应用的宝贵国家资源，锕系金属的化学对有效处理放射性废物至关重要。

This award in the Chemical Synthesis (SYN) program in the Division of Chemistry at NSF supports work by Professor William J. Evans at the University of California, Irvine, to carry out fundamental studies on redox reactions utilizing the unique properties of the lanthanide and actinide metals. These reduction/oxidation reactions constitute one of the two most basic types of chemical reactions and influence our lives in countless ways. Since the lanthanide and actinide elements represent extremes in the periodic table, they provide an excellent set of metals for expanding the limits of redox reactivity. Activation of small molecules like dinitrogen and nitric oxide will be studied since the redox chemistry of these molecules is critical to making the fertilizer that provides the food for the world and nitric oxide redox chemistry is also crucial to understanding topics as diverse as smog and vasodilation. The project will explore methods to access "virtual" oxidation states of metals that provide redox reactivity even though they have never been isolated. The ligands attached to metals will also be used to generate redox reactivity and develop molecules that can effect multi-electron redox processes. The latter are critical to reactions like solar water splitting that have the potential to provide clean energy without increasing carbon dioxide levels in the atmosphere.The pervasive nature of redox chemistry means that this research can have a broad impact on science and technology. At the same time, students will be trained in the chemistry of the lanthanide metals, which are a valuable national resource with numerous technological applications, and the actinide metals, whose chemistry is critical to efficient radioactive waste disposal.