Oxometal Complexes and Hydrocarbon Chemistry

该奖项是在无机，生物无机和 有机化学计划，以支持研究 克雷格湖埃默里大学的希尔。该奖项继续提供 支持Hill关于烃类催化氧化研究 过渡金属聚氧乙烯醚。热和 将研究光化学系统。这项工作将解决 氧的活化和转移的基本问题 从金属中心到C-H键和其他相关领域 工业和生物系统。 本研究的目的是：（1）建立 控制产物选择性，催化剂稳定性， 和持续的氧代转移的关键机制特征 烷烃催化均相，非常活跃和稳定， 抗氧化无机金属卟啉类似物 （2）开发手性IMA， 烷烃的不对称羟基化，（3）描绘 影响竞争量子产率的因素 多金属氧酸盐激发态衰减过程和 烃光氧化中的选择性和转换速率， (4)将未活化的C-H键转化为碳离子， 有用的反应，包括催化生产 - 直接从烃得到单氟化烃， 氟离子，和（5）严格建立结构， 光谱和光化学性质 聚过氧（氧代）钨酸盐， 用于微光刻的负性无机光致抗蚀剂 烯烃的选择性氧化剂。

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.