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Nitrosoarene-CuI complexes are intermediates in copper-catalyzed allylic amination
Radhey S Srivastava1, Masood A Khan, Kenneth M Nicholas
1Department of Chemistry, University of Louisiana at Lafayette, 70504, USA. rss1805@louisiana.edu
Journal of the American Chemical Society
|May 19, 2005
Summary
Novel copper(I) complexes with nitrosoarenes were synthesized and characterized. These complexes act as intermediates and potential catalysts in copper-catalyzed reactions, specifically the allylic amination of olefins.
Area of Science:
- Organometallic Chemistry
- Catalysis
- Synthetic Inorganic Chemistry
Background:
- Copper-catalyzed reactions are crucial in organic synthesis.
- Nitrosoarene ligands offer unique coordination possibilities.
- Understanding catalytic intermediates is key to reaction optimization.
Purpose of the Study:
- To synthesize and characterize novel homoleptic Cu(I)-nitrosoarene complexes.
- To investigate the structural properties of these complexes.
- To explore the role of these complexes in copper-catalyzed allylic amination.
Main Methods:
- Reaction of nitrosobenzene and N,N'-diethyl-4-nitrosoaniline with [Cu(CH3CN)4]PF6.
- X-ray crystallography for structural determination of complex 2.
- Reactions with olefins and dienes to probe catalytic activity.
Main Results:
- Successful synthesis of novel homoleptic Cu(I)-nitrosoarene complexes: [Cu(ArNO)3]PF6.
- X-ray structure of complex 2 shows a distorted trigonal planar copper coordination geometry.
- Complex 1 demonstrates intermediate behavior in Cu-catalyzed allylic amination, suggesting it as a potential nitrogen transfer agent.
Conclusions:
- Novel Cu(I)-nitrosoarene complexes can be synthesized and structurally characterized.
- These complexes serve as valuable intermediates in copper-catalyzed transformations.
- The findings provide insights into the mechanism of Cu-catalyzed allylic amination.
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