Mechanistic studies on pincer-complex reactivities with photo-chemical methodes

该研究项目的目的是对螯合物的不稳定反应中间体进行广泛的研究，这对ch活化和（脱）氢化反应很重要，并收集这些配合物上取代反应的动力学数据。这些物质和过程对于理解钳形复合物及其反应性非常重要，很难用经典方法检测到，但可以很容易地通过光化学来表征。因此，本研究是基于核磁共振光谱学的原位辐照探针，在约克大学独特的核磁共振光化学设置，经典的激光闪光光解实验和制备光化学技术。在预计的18个月的博士后研究项目中，调查将通过广泛的光化学研究拓宽对重要的钳型过渡金属配合物的机理理解。解离光化学可以帮助我们了解对ch活化和（去）氢化反应很重要的不稳定反应中间体的性质，以及钳形配合物上取代反应的一般动力学。通过提出的制备光化学实验，对钳形络合催化反应的典型底物的电子和空间性质进行分类应该是可能的。这可能成为这些催化剂定向优化的关键一步。

The aim of the proposed research project is to do an extensive study on labile reaction intermediates of pincer-complexes, important to CH-activation and (de)hydrogenation reactions, as well as the collection of kinetic data concerning substitution reactions at these complexes. These substances and processes, which are of immense importance for the understanding of pincer-complexes and their reactivity, are hard to detect by classical approaches but may easily be characterised via their photochemistry. Therefore this investigation is based on NMR spectroscopy with in situ irradiation in the probe, on the unique NMR photochemistry setup at the University of York, classical laser flash photolysis experiments and preparative photochemical techniques. During the 18 months anticipated for the postdoctoral research project, the investigations will broaden the mechanistic understanding of the important class of pincer-type transition metal complexes by an extensive photochemical study. The dissociative photochemistry should give insight into the properties of labile reaction intermediates important to CH-activation and (de)hydrogenation reactions as well as the general kinetics of substitution reactions on pincer complexes. With the proposed preparative photochemical experiments a classification of electronic and steric properties of typical substrates for pincer-complex catalysed reactions should be possible. This could become a crucial step forward for the directed optimisation of these catalysts.