Dioxygen Activation with Nickel Complexes

这个无机、生物无机和有机金属化学项目的奖项支持特拉华大学Charles G. Riordan教授的研究，以发展镍在其单价氧化状态下的配位化学，以激活二氧和相关的小分子。该方法将配位化学与光谱技术相结合，并辅以计算研究，以详细了解新型反应中间体的几何和电子结构。长期目标包括在有机分子的化学计量学和催化氧化中推进这些新物种。互补研究旨在激活单质硫和硒，以产生新的、可溶的Ni-S和Ni-Se结构。对较重的O2同系物S8和Se的相关研究补充了这些研究，为获得小分子/元素还原活化的比较见解提供了机会。该计划旨在通过系统的研究来解决结构、形成机制和固有反应性特征等问题，从而提高对镍基双氧活化的基本认识。本科生、研究生和博士后学生将在化学合成、厌氧和低温方法、先进的光谱方法和动力学等领域发展一系列技术技能，同时在当代无机化学的基本原理方面发展知识广度。与威斯康星-麦迪逊和加州-戴维斯实验室的互动将使学生接触到解决问题的合作方法。

This award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports research by Professor Charles G. Riordan at the University of Delaware to develop the coordination chemistry of nickel in its monovalent oxidation state to activate dioxygen and related small molecules. The approach combines coordination chemistry with spectroscopic techniques, augmented with computational studies, to generate a detailed understanding of geometric and electronic structures of novel reactive intermediates. Long-term objectives include advancing these new species in stoichiometric and catalytic oxidations of organic molecules. Complementary studies aim to activate elemental sulfur and selenium to produce new, soluble Ni-S and Ni-Se structures Related studies of the heavier O2 congeners, S8 and Se, complement these studies affording the opportunity to gain comparative insight into small molecule/element reductive activation. This program aims to advance the fundamental understanding of nickel-based dioxygen activation through systematic studies designed to address issues of structure, mechanism of formation and inherent reactivity characteristics. Undergraduate, graduate and postdoctoral students will develop a range of technical skills in areas including chemical synthesis, anaerobic and cryogenic methodologies, advanced spectroscopic methods and kinetics while developing intellectual breadth in the underlying principles of contemporary inorganic chemistry. Interactions with laboratories at Wisconsin-Madison and California-Davis will expose students to collaborative approaches in problem solving.