Projekt D

Heavy (5d) transition metals (TM) are important for many catalytic transformations, such as oxo/nitrene transfer. Owing to the transient character of the TM oxo/nitrene key intermediates, mechanistic evaluation of such reactions heavily relies on computational analysis. We want to benchmark the thermochemistry of 5d TM complexes relevant to catalysis, specifically with respect to spin-orbit relativistic contributions, which can be as large as 50 kcal/mol for bare transition metal ions in the gas phase. We will systematically evaluate the thermochemistry of hydrogen atom transfer to late 5d TM oxo/imido complexes as a key reaction to oxo/nitrene transfer catalysis via a radical rebound mechanism. This will allow for assessing the relevance of relativistic spin-orbit effects in the condensed phase and benchmarking of the computational methods.