Dioxygen Activation with Nickel Complexes

用镍络合物活化分子氧

• 批准号: 0809603
• 负责人: Charles Riordan
• 金额: $ 42万
• 依托单位: University of Delaware
• 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: 2008-09-01 至 2012-01-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0809603&HistoricalAwards=false
• 关键词: Dioxygen; Activation; Nickel; Complexes

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.

这个奖项在无机，生物无机和有机化学计划支持研究教授查尔斯G。Riordan在特拉华州大学开发镍在其单价氧化态下的配位化学，以激活分子氧和相关的小分子。该方法结合配位化学与光谱技术，增强与计算研究，以产生一个详细的了解几何和电子结构的新型活性中间体。长期目标包括在有机分子的化学计量和催化氧化中推进这些新物种。补充研究旨在激活元素硫和硒，以产生新的可溶性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，为获得对小分子/元素还原激活的比较深入的了解提供了机会。该计划旨在通过旨在解决结构，形成机制和固有反应特性问题的系统研究，推进对镍基分子氧活化的基本理解。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，同时发展当代无机化学基本原理的知识广度。 与威斯康星-麦迪逊和加利福尼亚-戴维斯实验室的互动将使学生接触到解决问题的协作方法。