Oxometal Complexes and Redox Chemistry

氧化金属配合物和氧化还原化学

基本信息

批准号：
8715322
负责人：
Craig Hill
金额：
$ 17.88万
依托单位：
Emory University
依托单位国家：
美国
项目类别：
Continuing Grant
财政年份：
1987
资助国家：
美国
起止时间：
1987-11-15 至 1991-04-30
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=8715322&HistoricalAwards=false
关键词：
Oxometal Complexes Redox Chemistry

项目摘要

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.

这项研究的重点是使用多氧盐和其他无机氧量生物，它们本身对氧化具有抵抗力，以催化低反应性的有机化合物的氧化还原转化，例如烷烃。直接的目标是确定这些催化碳氢化合物功能化系统稳定性的起源，并通过动力学，光谱和结构研究来确定这些过程的机械和结构反应特征。这些新的基于多氧的催化光化学过程不仅相对于烷烃功能化，而且还具有辐射能的转化和存储。这项工作应导致现有过程的改善，新光谱现象的描述以及新的催化过程的发展。基于多氧释放酸酯，有两种类型的均质催化烃官能化过程。首先涉及烷烃的光化学功能，并与光同时转化为化学能的可能有用的合成转化。第二个涉及将氧和相关组的热转移到碳氢化合物中。各种有机底物和多氧计之间几种最近记录的相互作用的物理，光化学和光物理属性将通过Picsecond和其他光谱研究，X射线晶体学和光化学实验探测。可溶性氧气物种对有机和无机分子的氧化还原转化的氧化物。