Photocatalytic Redox-neutral Aryl-diazene Synthesis via Dinitrogen Fixation

点击翻译按钮获取中文摘要

We aim to establish a method to activate molecular dinitrogen by one electron reduction for the direct reaction with organic aromatic compounds. Our proposed approach builds on the special properties of modified diamond surfaces, which upon excitation can expel electrons into aqueous solutions due to their negative electron affinity. Earlier studies have shown, that these solvated electrons react with dinitrogen yielding, after protonation, the reactive N2H radical. We strive to trap these reactive intermediates by reaction with aromatic hydrocarbons. In a redox neutral process dinitrogen is inserted into a C-H bond giving diazene molecules that can serve as platform chemical for a variety of important organic amino compounds. The photogeneration of solvated electrons from diamond is currently only possible by UV irradiation as a result of the very large bandgap of 5.47 eV. In this project, we aim for the use of visible light. This requires extensive bandgap engineering of the diamond material. Several strategies including nanostructuration, surface functionalization and doping and the formation of hybrid diamond materials will be pursued to introduce the required intra-bandgap states. The reactor design will be tailored to enable the use of a two-phase system for the generation of solvated electrons and their extraction into an organic phase by reaction with suitable arenes.