Multi-Electron Chemistry from d0 Metals and Redox-Active Ligands

在这个由化学系化学合成计划资助的项目中，加州大学欧文分校化学系的Alan Heyduk教授将开发氧化还原活性钳形配体的早期过渡金属化学。氧化还原活性配体提供了一种促进传统上不能进行氧化还原反应的金属中心处的多电子反应性的方法。Heyduk教授的研究工作将侧重于了解金属选择和配体取代基对这些新型配体的氧化还原性质以及金属中心小分子活化能力的影响。配体衍生物的系统合成将通过详细的光谱、电化学和计算研究来补充，以发展对氧化还原活性配体和配位金属离子之间的电子相互作用的更深入的理解。拟议的工作可能导致新的均相催化剂用于小分子反应，如水氧化、制氢和C-H键官能化。前两个领域的成功可能会影响太阳能和风能等替代能源解决方案的储能战略。C-H键官能化的成功将对化学合成的任何领域产生影响，其中期望以原子经济的方式利用低成本、容易丰富的化学原料。拟议的工作还将为下一代科学家提供基础化学科学和下一代替代能源化学方面的培训。

In this project funded by the Chemical Synthesis Program of the Chemistry Division, Professor Alan Heyduk of the Department of Chemistry at the University of California, Irvine will develop the early transition metal chemistry of redox-active, pincer ligands. Redox-active ligands provide a method for facilitating multi-electron reactivity at metal centers that are traditionally incapable of redox reactivity. Professor Heyduk's research effort will focus on understanding the impact of metal choice and ligand substituent on both the redox properties of these novel ligands as well as the capacity for small molecule activation at the metal center. Systematic synthesis of ligand derivatives will be complemented by detailed spectroscopic, electrochemical, and computational studies to developing a deeper understanding of the electronic interactions between redox-active ligands and coordinated metal ions.The proposed work could lead to new homogeneous catalysts for small molecule reactions such as water oxidation, hydrogen production and C-H bond functionalization. Success in the former two areas could impact energy storage strategies for alternative energy solutions such as solar and wind. Success in C-H bond functionalization would have an impact on any area of chemical synthesis in which it is desirable to utilize low-cost, readily abundant chemical feedstock in an atom-economical way. The proposed work will also provide training in both fundamental chemical sciences and in next-generation alternative energy chemistry to the next generation of scientists.