Oxometal Complexes and Hydrocarbon Chemistry

该奖项由无机化学、生物无机化学和金属有机化学项目颁发，以支持埃默里大学克雷格·L·希尔的研究。该奖项为希尔关于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。我们将研究热和光化学系统。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。本研究的目的是：(1)确定均相、高活性、高稳定性、抗氧化性的无机金属卟啉类似物(IMA)催化持续氧代转化为烷烃过程中控制产物选择性、催化剂稳定性和关键机理的因素。(2)开发将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盐激发态衰减过程的量子产率的因素以及烃类光氧化中的选择性和转化率，(4)将未活化的C-H键转化为碳离子，用于有用的反应，包括由碳氢化合物和氟离子直接催化生成单氟化氢；及(5)严格确定结构，聚过氧(氧)钨酸盐的光谱和光化学性质，它们有可能用作微影光刻的负性无机光致抗蚀剂和作为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.