Linear Free Energy Relationships (LFERs) are valuable tools for guiding catalyst selection and design. The isolation and quantification of ligand effects constitute critical steps towards constructing LFERs. Although LFERs have been successful in guiding the design of heterogeneous/supported catalysts, its study in homogeneous transition-metal chemistry is rare due to the complexity of mechanisms and the difficulties in deconvoluting electronic and steric and effects. Adopting methane conversion catalyzed by dioxo-dicopper complexes as the probing reaction, this study establishes a quantitative procedure to isolate electronic and geometric effects of steric bulk and utilizes these outcomes to develop linear free energy relationships along the lines of the Taft equation in organic chemistry. For more details, see this poster.
Animation of methane conversion
Students: Ryan