Oxometal Complexes and Hydrocarbon Chemistry

该奖项由无机、生物无机和有机金属化学项目颁发，以支持埃默里大学克雷格·l·希尔的研究。该奖项为Hill对过渡金属多金属氧酸盐催化碳氢化合物氧化的研究提供了持续的支持。热系统和光化学系统都将被研究。这项工作将解决从金属中心到C-H键的氧的活化和转移以及与工业和生物系统相关的其他领域的基本问题。本研究的目的是：(1)建立控制产物选择性、催化剂稳定性的因素，以及由均相、非常活跃和稳定、抗氧化的无机金属卟啉类似物（IMAs）催化的持续氧转移到烷烃的关键机理特征；(2)开发催化烷烃不对称羟基化的手性IMAs；(3)描述影响竞争多金属氧酸激发态衰变过程的量子产率以及烃光氧化的选择性和周转率的因素；(4)将未活化的C-H键转化为碳离子，用于有用的反应，包括直接由碳氢化合物和氟离子催化生产单氟化碳氢化合物；(5)严格建立结构，聚过氧（氧）钨酸盐的光谱和光化学性质，有潜力用作微光刻的无机负光刻剂和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.