Catalytic Mechanism of H₂ Activation by a Carbenoid Aluminum Complex

The catalytic mechanism of H₂ activation by a carbenoid aluminum compound is analyzed in great detail. On the basis of the reaction force analysis, the electronic activity that takes place during the chemical reaction was identified and characterized through the reaction electronic flux and rationalized in terms of chemical events that drive the reaction. Successive transformation of the nucleophilic or electrophilic character of the reagents along the reaction coordinate monitored through the dual descriptor allows us to obtain a very complete and detailed description of the reaction mechanism that proceeds through a two-stage mechanism in a one-kinetic-step process

Reaction Electronic Flux Perspective on the Mechanism of the Zimmerman Di-π-methane Rearrangement

The reaction electronic flux (REF) offers a powerful tool in the analysis of reaction mechanisms. Noteworthy, the relationship between aromaticity and REF can eventually reveal subtle electronic events associated with reactivity in aromatic systems. In this work, this relationship was studied for the triplet Zimmerman di-π-methane rearrangement. The aromaticity loss and gain taking place during the reaction is well acquainted by the REF, thus shedding light on the electronic nature of reactions involving dibenzobarrelenes