The Diaconescu Group: Redox switchable catalysis
Electrophilic Metal Centers for
Small Molecule Activation
Chem. Commun. 2019, 55, 7021-7024. “Computational mapping of redox-switchable metal complexes based on ferrocene derivatives”.
The selectivity of zirconium-ferrocene complexes for hydroamination-cyclization is altered through redox chemistry. The reduced species is able to cyclize primary amino alkenes and not secondary alkenes, while the oxidized species is active for secondary amino alkenes and not primary alkenes. This discovery of orthogonal reactivity will assist in the development of redox-switchable catalysts for tandem reactions.
J. Am. Chem. Soc. 2020, 142, 21292-21297.
The first dithorium arene inverse sandwich complex is reported joining the library of known f-group inverse sandwhich complexes. The complexes show evidence of delta-bonding interactions. The complexes prove to be potent 4 electron reductants capable of reducing a variety of alkenes, alkynes and azides. This multi-electron, redox activity will be further studied for difficult, small molecule transformations.
Acc. Chem. Res. 2019, 52, 415. “Redox-switchable Ring-Opening Polymerization with Ferrocene Derivatives”.
After building up a library of redox-switchable catalysts, the next step was to use the data therein to develop a computational model to understand how the metal, ligand and oxidation state determine the likelihood of polymerization. Models were able to identify the most important sites for future catalyst modification and optimization.