Bens, TobiasWalter, Robert R. M.Beerhues, JuliaLücke, ClemensGabler, JuliaSarkar, Biprajit2024-06-192024-06-1920231521-37650947-65391893932095http://nbn-resolving.de/urn:nbn:de:bsz:93-opus-ds-145672http://elib.uni-stuttgart.de/handle/11682/14567http://dx.doi.org/10.18419/opus-14548In recent years, metal complexes of pyridyl‐mesoionic carbene (MIC) ligands have been reported as excellent homogeneous and molecular electrocatalysts. In combination with group 9 metals, such ligands form highly active catalysts for hydrogenation/transfer hydrogenation/hydrosilylation catalysis and electrocatalysts for dihydrogen production. Despite such progress, very little is known about the structural/electrochemical/spectroscopic properties of crucial intermediates for such catalytic reactions with these ligands: solvato complexes, reduced complexes and hydridic species. We present here a comprehensive study involving the isolation, crystallographic characterization, electrochemical/spectroelectrochemical/theoretical investigations, and in‐situ reactivity studies of all the aforementioned crucial intermediates involving Cp*Rh and pyridyl‐MIC ligands. A detailed mechanistic study of the precatalytic activation of [RhCp*] complexes with pyridyl‐MIC ligands is presented. Intriguingly, amphiphilicity of the [RhCp*]‐hydride complexes was observed, displaying the substrate dependent transfer of H+, H or H-. To the best of our knowledge, this study is the first of its kind targeting intermediates and reactive species involving metal complexes of pyridyl‐MIC ligands and investigating the interconversion amongst them.eninfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by/4.0/540article2024-04-25