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Updated: May 6, 2026

Photogeneration of N-Heterocyclic Carbenes: Application in Photoinduced Ring-Opening Metathesis Polymerization
Published on: November 29, 2018
Photoactive Iminobismuthanes for Catalytic C-H Amination
Takuya Tsuruta1, Hye Won Moon1, Markus Leutzsch1
1Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, Mülheim an der Ruhr 45470, Germany.
Bismuth catalysts enable direct amination of C-H bonds, a feat previously limited to transition metals. This discovery opens new avenues in main-group catalysis for C-N bond formation.
Area of Science:
- Organometallic Chemistry
- Main-Group Chemistry
- Catalysis
Background:
- Metal-nitrenoids are crucial for direct amination of carbon-hydrogen (C-H) bonds.
- Transition metal catalysis typically relies on d-orbitals for redox and coordination flexibility.
- The role of main-group elements in such catalysis is underexplored.
Purpose of the Study:
- To investigate the catalytic potential of bismuth, a main-group element lacking accessible d-orbitals, in C-H amination.
- To demonstrate that main-group elements can exhibit catalytic activity comparable to transition metals.
- To explore novel reactivity enabled by bismuth's unique electronic properties.
Main Methods:
- Photochemical activation of iminobismuthanes.
- Ligand-to-ligand charge transfer (LLCT) mechanism.
- C-H bond abstraction and C-N bond formation reactions.
Main Results:
- Bismuth-based iminobismuthanes exhibit catalytic activity in direct C-H amination.
- Light irradiation triggers LLCT, initiating C-H abstraction and C-N bond formation.
- Demonstrated unique reactivity, including azidation of unprotected secondary amines, beyond transition metal capabilities.
Conclusions:
- Main-group imidos are catalytically active species, not just precursors.
- Bismuth catalysis offers a complementary approach to transition metal catalysis for C-N bond formation.
- This work expands the scope of main-group elements in catalysis.
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