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Catalysis with Palladium(I) Dimers
Christoph Fricke1, Theresa Sperger1, Marvin Mendel1
1Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074, Aachen, Germany.
Angewandte Chemie (International Ed. in English)
|October 15, 2020
Summary
Dinuclear palladium(I) complexes offer stable and robust catalytic frameworks. These complexes enable unique C-C and C-heteroatom bond formations, expanding catalytic possibilities beyond traditional palladium(0)/palladium(II) systems.
Area of Science:
- Organometallic Chemistry
- Catalysis
- Synthetic Organic Chemistry
Background:
- Dinuclear palladium(I) complexes are versatile catalysts for various transformations.
- Early applications focused on their role as pre-catalysts for palladium(0) species in cross-coupling reactions.
- Traditional palladium(I) dimers are often labile and oxygen-sensitive.
Purpose of the Study:
- To review the advancements in stable dinuclear palladium(I)-palladium(I) frameworks.
- To highlight their unique reactivity and catalytic applications.
- To discuss their mechanistic intricacies, speciation, and impact on reactivity.
Main Methods:
- Review of literature on dinuclear palladium(I) catalysis.
- Analysis of mechanistic studies on palladium(I) complexes.
- Discussion of reactivity profiles in C-C and C-heteroatom bond formations.
Main Results:
- Development of stable, bench-stable, and robust dinuclear palladium(I) frameworks.
- Demonstration of privileged reactivities through dinuclear catalysis.
- Selective C-C and C-heteroatom bond formations with poly(pseudo)halogenated arenes.
- Facilitation of arene couplings with weak nucleophiles, inaccessible to Pd(0)/Pd(II) catalysis.
- Utilization as pre-catalysts for active Pd(0) and Pd(II)-H species.
Conclusions:
- Stable dinuclear palladium(I) complexes offer significant advantages over traditional labile dimers.
- These frameworks enable novel catalytic pathways and expand the scope of palladium catalysis.
- Understanding mechanistic details is crucial for optimizing dinuclear palladium(I) catalysts.
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