Investigation of High Oxidation States by Matrix-Isolation Spectroscopy in Neat Fluorine Matrices

我们提议在阿尔伯特-路德维希斯Universität弗莱堡<s:1>有机体和分析化学研究所进行的研究主要是为了发展高度氧化过渡金属的化学性质。主要的重点将是基质分离光谱，氟化学和量子化学计算，可以概括为“计算机辅助合成的高度氧化物质”。根据这一指南，我们计划通过最先进的量子化学计算来研究高度氧化分子或中间体的热化学和动力学稳定性。基于计算，将选择可能的候选者进行拟议的矩阵隔离实验。由于我们的目标是高度氧化的物种，我们喜欢在整齐的氟基质中开发有问题的分子的合成。例如，将纯氟基与激光烧蚀金属一起应用，将所研究的过渡金属推向其最高氧化极限。例如，这种新方法应该会大大扩展高价氟化合物这一研究很少的领域的化学，以及我们对过渡金属物种在最高氧化态和配位极限下的理解。这绝不仅仅是学术上的兴趣，因为一些工业过程直接或作为中间体使用高度氧化的物质，其确切机制经常仍在争论中，因此需要进一步研究。

The research that we propose to undertake at the Albert-Ludwigs Universität Freiburg at the Institut für Anorganische und Analytische Chemie is primarily aimed at developing the chemistry of highly oxidized transition metals. The dominate emphasis will be on matrix-isolation spectroscopy, fluorine chemistry and quantum-chemical calculations and can be summarized as “Computer Aided Synthesis of Highly Oxidized Species”. Accordingly to this guideline we have planned to investigate thermochemical and kinetic stabilities of highly oxidized molecules or intermediates by state-of-the-art quantum-chemical calculations. Based on the calculations, possible candidates will be chosen for the proposed matrix-isolation experiments. As we are aiming for highly oxidized species, we like to develop the synthesis of the molecules in question in neat fluorine matrices. For instance the application of neat fluorine matrices together with laser ablated metals will push the transition metals under investigation to their highest oxidation limit. This new approach for example should result in a significant extension of the chemistry of this little studied field of high-valent fluorine compounds and our understanding of transition metal species in their highest oxidation states and at the limits of coordination. This is by no means only of academic interest, because several industrial processes employ highly oxidized species directly or as intermediates, and the precise mechanism is often still under debate and therefore demands further investigation.