The Miller Group: Organometallic chemistry
Pincer-crown Ether Complexes for Cation-Controlled Catalysis
Kita, M. R.; Miller, A . J. M. “An Ion-Responsive Pincer-Crown Ether Catalyst System for Rapid and Switchable Olefin Isomerization.” Angew. Chem. Int. Ed. 2017, 56, 5498-5502.
In this work, we demonstrate cation-tunable olefin isomerization with a pincer-iridium complex functionalized with a crown ether moiety. Catalysis is both switchable and tunable: the iridium complex can be switched on and off via halide addition and halide abstraction; and the rate of catalysis can be dramatically increased by addition of alkali metal salts.
Nitrogen Reduction to Ammonia
Bruch, Q. J.; Connor G.P.; Chen, C.; Holland, P. L.; Mayer, J. M.; Hasanayn, F.; Miller, A. J. M. “Dinitrogen Reduction to Ammonium at Rhenium Utilizing Light and Proton-Coupled Electron Transfer.” J. Am. Chem. Soc. 2019, 141, 20198-20208.
We report a pincer-ligated rhenium system capable of reducing N2 to NH3. The reaction occurs via formation of a bridging N2 complex, photolytic N2 splitting, and proton-coupled electron transfer reduction of the resulting rhenium-nitride to generate NH3.
Stratakes, B.M.; Miller, A.J.M. “H2 Evolution at an Electrochemical “Underpotential” with an Iridium-Based Molecular Photoelectrocatalyst” ACS Catalysis, 2020, 10, 16, 9006-9018.
In this work, we investigate the parameters that govern electrochemical overpotential for H2 generation by iridium photoelectrocatalysts. Conditions were discovered that allow an iridium photoelectrocatalyst to generate H2 at an electrochemical "underpotential" using visible light.