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Strongly Coordinating Ligands To Form Weakly Coordinating Yet Functional Organometallic Anions
Steven P Fisher1, Scott G McArthur1, Varun Tej1
1Department of Chemistry and Center for Catalysis , University of California-Riverside , Riverside , California 92521 , United States.
Journal of the American Chemical Society
|December 6, 2019
Summary
Functional organometallic anions act as both weakly coordinating anions and catalysts. Novel polyhalogenated carboranyl NHCs enhance stability and catalytic activity in hydroamination reactions.
Area of Science:
- Organometallic Chemistry
- Catalysis
- Anion Design
Background:
- Weakly coordinating anions (WCAs) traditionally lack functional roles.
- N-heterocyclic carbenes (NHCs) are versatile ligands in organometallic chemistry.
Purpose of the Study:
- To develop strongly coordinating dianionic carboranyl NHCs as functional WCAs.
- To create novel organometallic -ate complexes of Au(I) with dual WCA and catalytic properties.
Main Methods:
- Synthesis of dianionic carboranyl NHCs and their Au(I) complexes.
- Development of polyhalogenated carboranyl NHCs for enhanced stability.
- Investigation of catalytic activity in hydroamination of alkynes.
Main Results:
- Formation of heterobimetallic and organometallic/main group ion pairs using organometallic WCAs.
- Demonstration of superior stability of polyhalogenated carboranyl NHCs.
- Achieved high catalytic activity in alkyne hydroamination.
- Reported first low-coordinate Au(III) center and first true dianionic carbene.
Conclusions:
- Organometallic WCAs can possess both spectator and catalytic functions.
- Polyhalogenated carboranyl NHCs offer enhanced stability and catalytic performance.
- These findings enable the design of functional ion pairs for cooperative catalysis.
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