Volcano plots for homogeneous Suzuki catalysts
Linear scaling of Suzuki intermediates yields volcano plots that place Ni/Pd/Pt near the top and coinage metals on the wrong slope.
Source
Linear scaling relationships and volcano plots in homogeneous catalysis - revisiting the Suzuki reaction
Study at a glance
- Design
- Computational / modelling — DFT free-energy scaling relations and volcano plots for a Suzuki catalytic cycle across ML2 complexes
- N
- Homogeneous-catalysis computational screen — no sample N
- Population
- ML2 catalyst models in a Suzuki coupling cycle
- Outcome
- Scaling relationships identifying near-ideal oxidative-addition energetics
Structured fields used in claim comparison tables when every cited study has a complete layer.
What they did
Authors computed a Suzuki catalytic cycle for many ML2 complexes, built linear free-energy scaling relations among intermediates, and plotted −ΔG(pds) versus a descriptor intermediate as in heterogeneous catalysis.
What they found
The cycle free energy is −67.9 kcal mol−1; an ideal oxidative addition is −11.3 kcal mol−1. Pd(PMe3)2 sits near the ideal line, Pd(CO)2 is too weakly bound (−5.9), and Pd(NH3)2 is overbound (−44.0). Group 10 metals outperform Cu, Ag, and Au. Intermediate 3 vs 2 scales with R2 = 0.98.
The limits
What it doesn't show
The volcano is thermodynamic screening, not a full kinetic microkinetic model or a newly synthesized catalyst; barriers and solvent sampling are secondary.
Key terms
- Volcano plot
- Activity versus descriptor that peaks when binding is neither too weak nor too strong (Sabatier).
- Linear scaling relation
- Correlation of intermediate free energies so one descriptor predicts the rest.
- Potential-determining step
- The least favorable ΔG among cycle steps, used as the volcano height.
- Suzuki coupling
- Pd-catalyzed C–C coupling used here as a homogeneous test reaction.
- ΔGRRS
- Relative free energy of a catalytic intermediate used as the volcano descriptor.
Flashcards
Research intelligence for this paper
See its role on concept claims, tensions it is part of, placement history, and related discoveries.
Quiz yourself
Volcano plots here are applied to:
Common questions
Do heterogeneous volcano tools work for Suzuki?
Yes—they reproduce known homogeneous trends.
Which metals sit high on the volcano?
Group 10 (Ni, Pd, Pt), not coinage metals.
What is the Sabatier idea?
The ideal catalyst binds neither too weakly nor too strongly.
Example of a balanced catalyst?
Pd(PMe3)2 follows the ideal thermodynamic line.
More on Computational chemistry