The unsubstituted iron–oxo porphyrin reacts with unsubstituted benzylic C–H bond substrates via a synchronous HAT mechanism. In contrast, when an electron-rich iron–oxo porphyrin reacts with electron-poor substrates, it follows a basic asynchronous HAT mechanism.
A comprehensive theoretical investigation of CO2 electroreduction catalyzed by pyrox- and bpy-Mn complexes reveals that the synergistic modulation of axial and heterocyclic ligands enables low overpotential and high catalytic activity.
A suitable model for computational study giving reliable estimation of the catalytic effect of σ-hole donating organocatalysts is suggested.
Chalconium and halonium salts catalyze Schiff condensation. Kinetic data and DFT calculations show that the catalytic activity correlates with maximum electrostatic potential on σ-holes, whereas other factors are less significant.
To study whether the use of substrate descriptors to rationalize a catalytic outcome may be an effective tool, we investigated both an encapsulated and non-encapsulated rhodium based catalyst in the hydroformylation reaction of 41 terminal alkenes.