Expanding Reductive Chemistry with the f Orbital Metals

美国国家科学基金会化学部化学合成(SYN)项目的这一奖项支持加州大学欧文分校的William J.Evans教授利用镧系元素和榄系元素金属的独特性质开展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之一，并以无数方式影响着我们的生活。由于镧系元素和榄系元素在元素周期表中代表极端，它们为扩大氧化还原反应的极限提供了一组极好的金属。将研究氮素和一氧化氮等小分子的激活，因为这些分子的氧化还原化学对于制造为世界提供粮食的肥料至关重要，而一氧化氮氧化还原化学对于理解烟雾和血管扩张等各种主题也至关重要。该项目将探索访问金属的“虚拟”氧化态的方法，这些金属具有氧化还原活性，即使它们从未被分离出来。附着在金属上的配体还将用于产生氧化还原反应能力，并开发能够影响多电子氧化还原过程的分子。后者对于像太阳能分解水这样的反应至关重要，这些反应有可能在不增加大气中二氧化碳水平的情况下提供清洁能源。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影响。同时，将对学生进行镧系金属化学方面的培训，这些金属是一种有价值的国家资源，具有许多技术应用，以及鳗系金属，其化学对有效处置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.