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Metal Electronics Mediate Steric and Coordination Number Effects on Palladium(II) C-X Reductive Elimination
Michael K Bogdos1, Sven Roediger1, Florian Ruepp1
1Laboratory of Organic Chemistry, Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog-Weg 3, 8093 Zürich, Switzerland.
This study reevaluates reductive elimination rates in metal catalysis, finding metal electronics and coordination number changes are key drivers, not coordination number alone. This leads to a predictive model for bond formation reactions.
Area of Science:
- Organometallic Chemistry
- Catalysis
- Computational Chemistry
Background:
- Reductive elimination is crucial for synthesizing pharmaceuticals, materials, and fine chemicals via transition metal catalysis.
- Factors influencing reductive elimination rates include metal electronics, ligand sterics, and coordination number, but their relative importance is unclear.
Purpose of the Study:
- To quantify the influence of metal electronics, ligand sterics, and coordination number on reductive elimination rates.
- To reexamine the canonical model of reductive elimination and propose an updated mechanistic understanding.
Main Methods:
- Kinetics studies
- Electrochemistry
- Density Functional Theory (DFT) calculations
- Causal inference and mediation analysis
Main Results:
- A direct effect of coordination number on reductive elimination rate is unlikely.
- Metal electronics and changes in coordination number are the primary drivers of the reaction rate.
- Coordination number influences the rate mainly by altering metal electronics.
Conclusions:
- An updated mechanistic model for reductive elimination is proposed, integrating new findings with existing literature.
- A predictive model using DFT descriptors can accurately estimate reductive elimination rates for C-N, C-S, and C-O bond formation.
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