Organometallic Chemistry

Linking Mechanistic Analysis of Catalytic Reactivity Cliffs to Ligand Classification


Statistical analysis of reaction data with molecular descriptors can enable chemists to identify reactivity cliffs that result from a mechanistic dependence on a specific structural feature. In this study, we develop a broadly applicable and quantitative classification workflow that identifies reactivity cliffs in eleven Ni- and Pd-catalyzed cross-coupling datasets employing monodentate phosphine ligands. A unique ligand steric descriptor, %Vbur (min), is found to divide these datasets into active and inactive regions at a similar threshold value. Organometallic studies demonstrate that this threshold corresponds to the binary outcome of bisligated versus monoligated metal and that %Vbur (min) is a physically meaningful and predictive representation of ligand structure in catalysis. Taken together, we expect that this strategy will be of broad value in mechanistic investigation of structure-reactivity relationships, while providing a means to rationally partition datasets for data-driven modeling.

Version notes

version draft one


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Supplementary material

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VBur Threshold SI f
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DFT xyz coodinates
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mo PDJSNS23 0m
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mo PDJSNS13 0m
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mo PDJSNS12 0m
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mo PDJSNS9 0m