| Autor: |
Bens, Tobias, Walter, Robert R. M., Beerhues, Julia, Lücke, Clemens, Gabler, Julia, Sarkar, Biprajit |
| Předmět: |
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| Zdroj: |
Chemistry - A European Journal; 1/11/2024, Vol. 30 Issue 3, p1-16, 16p |
| Abstrakt: |
In 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. [ABSTRACT FROM AUTHOR] |
| Databáze: |
Complementary Index |
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