Oxometal Complexes and Redox Chemistry

本研究的重点是利用多金属氧酸盐和其他本身抗氧化的无机金属氧，催化低反应活性的有机化合物，如烷烃的氧化还原转化。当前的目标是建立这些催化烃类功能化系统稳定性的起源，并通过动力学、光谱和结构研究确定这些过程的机理和结构反应性特征。这些新的基于多金属氧酸盐的催化光化学工艺不仅在烷烃功能化方面具有潜在的用途，而且在辐射能的转换和储存方面也具有潜在的用途。这项工作将导致现有工艺的改进，新的光谱现象的描述，以及新的催化过程的发展。目前已有两种基于多金属氧酸盐的均相催化烃类功能化工艺。第一个涉及烷烃的光化学功能化，以及将潜在有用的合成转化与光转化为化学能的同时耦合。第二个过程涉及氧和相关基团转化为碳氢化合物的热传递。几种最近记录的有机基质与多金属氧酸盐之间相互作用的物理，光化学和光物理属性将通过皮秒和其他光谱研究，x射线晶体学和光化学实验进行探测。这些实验有望进一步揭示可溶性金属氧化物在有机和无机分子氧化还原转化中的潜在应用。

The focus of this research is the use of polyoxometalates and other inorganic oxometal species, which are themselves resistant to oxidation, to catalyze redox transformations of organic compounds of low reactivity, such as alkanes. The immediate goals are to establish the origins of the stability of these catalytic hydrocarbon functionalization systems and to determine the mechanistic and structure-reactivity features of these processes by kinetics, spectroscopic and structural studies. These new polyoxometalate-based catalytic photochemical processes are of potential utility with respect to not only alkane functionalization but also the conversion and storage of radiant energy. The work should lead to improvements in the existing processes, delineation of new spectroscopic phenomena, and development of new catalytic processes. There have been two types of homogeneous catalytic hydrocarbon functionalization processes based on polyoxometalates. The first involves the photochemical functionalization of alkanes, and coupling potentially useful synthetic transformations with the simultaneous conversion of light into chemical energy. The second involves the thermal transfer of oxo and related groups into hydrocarbons. The physical, photochemical and photophysical attributes of several recently documented interactions between various classes of organic substrates and polyoxometalates will be probed by picosecond and other spectroscopic studies, X-ray crystallography and photochemical experiments.These experiments are expected to yield further information on the potential applications of soluble oxometal species to redox transformations of organic and inorganic molecules.