Activation Barriers of Co(IV)-centered Reductive-Elimination Correlate with Quantified Interatomic Noncovalent Interactions.

Activation Barriers of Co(IV)-centered Reductive-Elimination Correlate with Quantified Interatomic Noncovalent Interactions.

| Lucas Loir-Mongazon, Carmen Antúfa-Hörlein, Christophe Deradet, Yann Cornaton, Jean-Pierre Djukic
This study investigates the weak interligand noncovalent interactions within Co(IV)-catalyzed redox-elimination reactions using the Independent Gradient Model/Intrinsic Bond Strength Index (IGM/IBSI) method. The activation barriers of the desired reductive elimination (RE) pathway are found to correlate directly with the IBSI of the X-to-carbanionic chelate's carbon. This correlation suggests that predicting which -X ligand is more prone to efficient Cp*Co-catalyzed directed X-functionalization of aromatic C-H bonds is feasible. The study also includes a series of experiments with various -X ligands to validate the theoretical conclusions. The results indicate that the Co(III)-to-Co(IV) oxidation lowers the activation barrier for RE, and the nature of the X ligand significantly affects the reactivity, with stronger C2-X interactions correlating with lower RE activation barriers. Experimental data supports these theoretical findings, showing that complexes with higher IBSI(C2'-X) values tend to undergo RE, while those with lower IBSI(C2'-X) values favor other pathways like hydro-de-metalation or cyclocondensation.This study investigates the weak interligand noncovalent interactions within Co(IV)-catalyzed redox-elimination reactions using the Independent Gradient Model/Intrinsic Bond Strength Index (IGM/IBSI) method. The activation barriers of the desired reductive elimination (RE) pathway are found to correlate directly with the IBSI of the X-to-carbanionic chelate's carbon. This correlation suggests that predicting which -X ligand is more prone to efficient Cp*Co-catalyzed directed X-functionalization of aromatic C-H bonds is feasible. The study also includes a series of experiments with various -X ligands to validate the theoretical conclusions. The results indicate that the Co(III)-to-Co(IV) oxidation lowers the activation barrier for RE, and the nature of the X ligand significantly affects the reactivity, with stronger C2-X interactions correlating with lower RE activation barriers. Experimental data supports these theoretical findings, showing that complexes with higher IBSI(C2'-X) values tend to undergo RE, while those with lower IBSI(C2'-X) values favor other pathways like hydro-de-metalation or cyclocondensation.
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