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Introducing a mixed-valent dirhodium(II,III) catalyst with increased stability in C-H amination
Katherine P Kornecki1, John F Berry
1Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, WI 53713, USA.
A novel rhodium dimer catalyst facilitates intramolecular C-H amination, demonstrating high efficiency and expanding the utility of rhodium dimers in nitrenoid chemistry.
Area of Science:
- Inorganic Chemistry
- Organometallic Chemistry
- Catalysis
Background:
- Mixed-valent Rh(2)(II,III) dimers are known for catalytic applications.
- Expanding the scope of these dimers to new reaction types is of significant interest.
Purpose of the Study:
- To report a new mixed-valent Rh(2)(II,III) dimer complex.
- To investigate its catalytic activity in intramolecular C-H amination reactions.
Main Methods:
- Synthesis and characterization of the new rhodium dimer, [Rh(2)(espn)(2)Cl].
- Solution studies to determine the active catalytic species.
- Evaluation of catalytic performance in intramolecular C-H amination, including turnover number (TON) determination.
Main Results:
- The new compound [Rh(2)(espn)(2)Cl] readily forms the active [Rh(2)(espn)(2)](+) catalyst in solution.
- The catalyst exhibits high efficiency in intramolecular C-H amination, achieving turnover numbers greater than 1400.
- This represents a new application for Rh(2)(II,III) dimers.
Conclusions:
- A novel mixed-valent Rh(2)(II,III) dimer has been synthesized and characterized.
- The dimer serves as an effective precursor to a highly active catalyst for intramolecular C-H amination.
- This study broadens the application of rhodium dimers into nitrenoid chemistry.
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