Matrix Isolation and Theoretical Study of the Mechanisms of Oxidation Processes

在这个由化学部门实验物理化学项目支持的项目中，辛辛那提大学的Bruce Ault和扬斯敦州立大学的Janet Del Bene将使用基质分离光谱研究两类氧化还原反应。第一类由高价过渡金属含氧化合物组成，特别是氯化铬和甲基三氧鎓，第二类涉及有机过氧化物，以过氧化氢为原型。该项目的目标包括确定反应途径中的关键中间体，这些中间体的光谱和结构表征，将实验结果与高级理论计算进行比较，并推断这些反应的反应机理。反应中间体将被捕获并保存在低温惰性基质中，使用一系列沉积技术和不同形式的能量输入来引发反应。被捕获的物种将通过红外、拉曼和可见/紫外光谱进行表征。这个项目将有助于理解氧化反应的机制，这是目前催化研究的核心。有机物的氧化是工业中最重要的反应之一，但环境废物需要减少，原材料需要更好地保存。受这项工作影响的其他领域包括大气化学和空气污染、废水处理、精细化学品的生产和合成有机方法。

In this project supported by the Experimental Physical Chemistry Program of the Chemistry Division, Bruce Ault of the University of Cincinnati and Janet Del Bene of Youngstown State University will study two classes of oxidation-reduction reactions using matrix-isolation spectroscopy. The first class consists of high-valent transition metal oxo compounds, specifically chromyl chloride and methyltrioxorhenium, and the second involves organic peroxides, with hydrogen peroxide as a prototype. The goals of this project include identification of key intermediates in the reaction pathways, spectroscopic and structural characterization of these intermediates, comparison of experimental results to high-level theoretical calculations, and deduction of the reaction mechanism for these reactions. The reactive intermediates will be trapped and preserved in cryogenic inert matrices using a range of deposition techniques and different forms of energy input to initiate reaction. Trapped species will be characterized by infrared, Raman, and visible/ultraviolet spectroscopy.This project will aid in understanding the mechanisms of oxidation reactions that are at the heart of current research into catalysis. Oxidation of organics constitutes one of the most important reactions in industry, but environmental waste needs to be decreased and raw materials to be conserved better. Other areas impacted by this work include atmospheric chemistry and air pollution, waste water treatment, the production of fine chemicals, and synthetic organic methodology.