Computational chemistry
Volcano plots for homogeneous Suzuki catalysts
Open access · cc by · source: Europe PMC
Linear scaling of Suzuki intermediates yields volcano plots that place Ni/Pd/Pt near the top and coinage metals on the wrong slope.
How this study connects
Role on claims
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Evidence for the claim as stated.
Linear scaling of Suzuki intermediates yields volcano plots that place Ni/Pd/Pt near the top and coinage metals on the wrong slope.
Evidence for the claim as stated.
Functional choice and static vs dynamics treatments change spin states, barriers and spectra; agreement on one molecule does not transfer automatically.
Evidence for the claim as stated.
Open questions
Tensions this paper is part of
From concept pages' “where studies disagree.” Disagreement means the same question; scope means different assays, populations, or outcomes.
Functional choice and static vs dynamics treatments change spin states, barriers and spectra; agreement on one molecule does not transfer automatically.
- Supports · Halogen bonds are not purely electrostatic
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.
Inspect source passages
Volcano plots for homogeneous Suzuki catalysts
These passages occur verbatim in the stored paper text. They support the points listed below; they do not verify every statement in the explanation.
Ideal oxidative addition is −11.3 kcal mol−1; Pd(CO)2 is only −5.9.
For Pd(CO) 2 , the value of oxidative addition is only –5.9 kcal mol –1 , considerably less than the –11.3 kcal mol –1 of the hypothetical ideal catalyst.
The Suzuki cycle free energy is fixed at −67.9 kcal mol−1.
Because the free energy to complete one catalytic cycle is fixed (–67.9 kcal mol –1 for the Suzuki coupling studied here) an oxidative addition step that is either overly or underly exergonic must be balanced elsewhere in the catalytic cycle.
Key findings
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.
Methodology
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.
Limitations
The volcano is thermodynamic screening, not a full kinetic microkinetic model or a newly synthesized catalyst; barriers and solvent sampling are secondary.
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