Oxometal Complexes and Hydrocarbon Chemistry

氧合金属络合物和碳氢化合物化学

• 批准号: 9022317
• 负责人: Craig Hill
• 金额: $ 26.11万
• 依托单位: Emory University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1991
• 资助国家: 美国
• 起止时间: 1991-03-01 至 1995-02-28
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9022317&HistoricalAwards=false
• 关键词: Oxometal; Complexes; Hydrocarbon; Chemistry

This award is made in the Inorganic, Bioinorganic and Organometallic Chemistry Program in support of the research of Craig L. Hill at Emory University. The award provides continued support for Hill's research on hydrocarbon oxidation catalyzed by transition metal polyoxometallates. Both thermal and photochemical systems will be studied. The work will address fundamental problems in the activation and transfer of oxygen from metal centers to C-H bonds and other areas of relevance to both industrial and biological systems. The objectives of the research are: (1) to establish the factors which control product selectivity, catalyst stability, and key mechanistic features in sustained oxo transfer to alkanes catalyzed by homogeneous, very active and stable, oxidatively-resistant inorganic metalloporphyrin analogues (IMAs), (2) to develop chiral IMAs that will catalyze asymmetric hydroxylation of alkanes, (3) to delineate the factors that affect the quantum yields of competing polyoxometallate excited state decay processes and the selectivities and turnover rates in hydrocarbon photooxidation, (4) to convert unactivated C-H bonds into carbonium ions for useful reactions including the catalytic production of monofluorinated hydrocarbons directly from hydrocarbons and fluoride ion, and (5) to rigorously establish the structural, spectroscopic and photochemical properties of polyperoxo(oxo)tungstates that have potential for use as negative inorganic photoresists for microlithography and as selective oxidants for olefins.

该奖项是在无机、生物无机和有机金属化学项目中颁发的，旨在支持埃默里大学 Craig L. Hill 的研究。该奖项为希尔在过渡金属多金属氧酸盐催化碳氢化合物氧化方面的研究提供了持续的支持。将研究热系统和光化学系统。这项工作将解决氧从金属中心活化和转移到 C-H 键以及与工业和生物系统相关的其他领域的基本问题。 研究的目标是：(1) 确定控制产物选择性、催化剂稳定性的因素，以及由均相、高活性和稳定、抗氧化的无机金属卟啉类似物 (IMA) 催化的持续氧代转移到烷烃的关键机制特征，(2) 开发可催化烷烃不对称羟基化的手性 IMA，(3) 描述影响竞争性量子产率的因素多金属氧酸盐激发态衰变过程以及烃光氧化中的选择性和周转率，（4）将未活化的C-H键转化为碳鎓离子，用于有用的反应，包括直接从烃和氟离子催化生产单氟化烃，以及（5）严格建立聚过氧化钨酸盐的结构、光谱和光化学性质，具有用作微光刻负性无机光刻胶和选择性氧化剂的潜力烯烃。