Nickel-Oxygen Chemistry: Synthesis and Reactivity

镍氧化学：合成和反应性

• 批准号: 1112035
• 负责人: Charles Riordan
• 金额: $ 44.18万
• 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: 2011
• 资助国家: 美国
• 起止时间: 2011-09-01 至 2015-01-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1112035&HistoricalAwards=false
• 关键词: Nickel; Oxygen; Chemistry; Synthesis; Reactivity

This award in the Chemical Synthesis (SYN) program supports work by Professor Charles G. Riordan at the University of Delaware to carry out fundamental studies on the reaction of nickel complexes with dioxygen. Using ligand design and chemical synthesis strategies, new nickel-superoxo, -alkylperoxo and -hydroperoxo complexes are sought. The geometric and electronic structures will be defined by applying a range of spectroscopic methods. Reactivity of the new molecules with exogenous substrates susceptible to oxygen atom transfer and C-H activation will be explored in an effort to correlate structure with reactivity. Complementary efforts are aimed at garnering evidence for high-valent oxonickel intermediates. These studies require that student coworkers develop intellectual breadth in synthetic and mechanistic inorganic chemistry and molecular alternative energy. They further afford students the opportunity to collaborate on advanced spectroscopic measurements with colleagues at the Universities of Wisconsin-Madison and California-Davis.Metal-mediated oxygen activation is a central process in Nature as well as the chemical and pharmaceutical industries. The development of new reagents using abundant, i.e. cheap metals, for stoichiometric and catalytic oxidation of organic molecules remains a significant challenge. The fundamental studies of this project will provide insight into how to harness the redox attributes of nickel for these chemical transformations.

化学合成（SYN）项目的这一奖项支持特拉华大学Charles G. Riordan教授对镍配合物与二氧反应的基础研究。利用配体设计和化学合成策略，寻求新的镍-超氧、-烷基-过氧和-氢-过氧配合物。几何和电子结构将通过应用一系列光谱方法来定义。新分子与外源底物的反应性易受氧原子转移和C-H活化的影响，将在努力将结构与反应性联系起来的过程中进行探索。补充工作旨在收集高价氧镍中间体的证据。这些研究要求学生同事在合成和机械无机化学以及分子替代能源方面发展知识广度。他们还为学生提供了与威斯康星大学麦迪逊分校和加州大学戴维斯分校的同事合作进行先进光谱测量的机会。金属介导的氧活化是自然界以及化学和制药工业的中心过程。开发新的试剂，利用丰富的，即廉价的金属，用于化学计量和催化氧化有机分子仍然是一个重大的挑战。该项目的基础研究将为如何利用镍的氧化还原属性进行这些化学转化提供见解。