Mapping Catalyst-Solvent Interplay in Competing Carboamination/Cyclopropanation Reactions.

Area of Science:

• Organometallic Chemistry
• Catalysis
• Chemical Synthesis

Background:

• Group 9 metals, specifically cyclopentadienyl rhodium(III) complexes, are effective C-H activation catalysts.
• Solvent choice critically impacts the outcome of Cp*Rh^III-catalyzed reactions between alkenes and N-enoxyphthalimides, favoring carboamination in methanol and cyclopropanation in 2,2,2-trifluoroethanol (TFE).

Purpose of the Study:

• To develop selectivity and activity maps for cyclopentadienyl metal catalysts (Cp^XM^III, M=Co, Rh, Ir) to understand catalyst-solvent interplay.
• To predict reaction outcomes for untested catalyst/solvent combinations and identify optimal experimental protocols.

Main Methods:

• Analysis of 42 cyclopentadienyl metal catalysts (Cp^XM^III).
• Creation of selectivity and activity maps to visualize catalyst-solvent interactions.
• Identification of Pareto front solutions for optimizing activity and selectivity.

Main Results:

• The maps successfully rationalize previously reported experimental results.
• Predictive power demonstrated for untested catalyst/solvent combinations.
• Demonstrated how Cp*Rh^III enables solvent-induced reactivity changes and quantified the impact of minor solvent variations.

Conclusions:

• Selectivity and activity maps offer a generalizable tool for predicting reaction outcomes across diverse metal, ligand, and solvent spaces.
• These maps facilitate the development of new experimental protocols for optimizing catalytic reactions.
• Understanding catalyst-solvent interactions is crucial for controlling reactivity and selectivity in C-H activation.