Jackson Research Group
Bioinorganic & Bio-inspired Chemistry
Roughly a third of all enzymes require metals to perform their biological functions. Plants use a manganese enzyme to transform water into oxygen. Our bodies use iron enzymes to transport oxygen, break down toxic molecules, and perform a host of other functions.
The Jackson Lab’s research helps to understand the details of these bioinorganic reactions. Our lab also uses these biological processes to develop environmentally-friendly, bio-inspired reactions that could be useful to the chemical industry.
Nature uses metalloenzymes containing Mn, Fe, or Cu and oxidants such as molecular oxygen and hydrogen peroxide to carry out remarkable oxidative transformations that are both vital for life and fascinating from a fundamental perspective. Such reactions also serve as inspiration for synthetic chemists, as catalytic processes that utilize earth-abundant metals are less expensive and more environmentally benign than conventional process that employ precious-metals. Our research focuses on using synthetic model complexes to understand the chemical reactions that are critical to the function of both metalloenzymes and earth-abundant metal catalysts. These reactions include activation of dioxygen and hydrogen peroxide and the cleavage of C-H and O-H bonds by high- and mid-valent metal-oxygen species. To achieve these goals, the Jackson lab uses a combination of i) synthetic and kinetic methods to generate and characterize the reactivity patterns of metal ion complexes, ii) detailed spectroscopic characterization of transition-metal species, and iii) computational chemistry. These combined efforts allow us to identify geometric and electronic properties of transition-metal complexes that influence chemical reactivity.
Spectroscopic methods used in our research include electronic absorption (UV-vis), electron paramagnetic resonance (EPR), magnetic circular dichroism (MCD), and X-ray absorption (XAS) spectroscopies. We also employ NMR methods to probe the solution structures of paramagnetic complexes. These tools are particularly powerful when used in conjunction with computational methods, as they permit the characterization of the geometric and electronic structures of fleeting intermediates too unstable to be characterized using standard crystallographic methods. Our lab also used kinetic studies to probe the reaction mechanisms of our complexes. By applying this three-pronged approach to bio-inspired transition-metal complexes, we gain detailed insight into how nature uses molecular oxygen and earth-abundant metals to oxidize substrates and apply this knowledge to develop transition metal complexes that can perform green oxidation reactions.
The Jackson lab has on-going collaborations with a variety of labs, where we bring our expertise in spectroscopic and computational methods to learn about the electronic structure and chemical reactivity of transition-metal complexes.
Josh Telser (Roosevelt University, Chicago): A variety of projects with Prof. Telser have focused on using unique spectroscopic methods and electronic structure computations to understand optical and magnetic properties of coordination complexes. Representative Publication
Dong Wang (University of Montana): Our collaboration with Prof. Wang’s lab is focused on the electronic structure and reactivity of Co complexes in unusually high oxidation states. While rare, high-valent Co complexes are presumed intermediates in a variety of Co catalysts. Representative Publication
Elodie Anxolabéhère-Mallart (Université Paris, Diderot): Our long-standing collaboration with Prof. Anxolabéhère-Mallart has entailed using electrochemical methods in the Anxolabéhère-Mallart to investigate the reactions of Mn(II) complexes with electrochemically-generated superoxide. These methods have permitted new understanding of the oxidation-reduction reactions of peroxomanganese(III) complexes. Such complexes are important intermediates in manganese enzymes and synthetic oxidation catalysts. Representative Publication
Carole Duboc (Univ. Grenoble Alpes): Our recent collaboration with Prof. Duboc’s lab is aimed at developing new transition-metal complexes that react with molecular oxygen.