1567 Irving Hill Rd
Lawrence, KS 66045
- Bioinorganic Chemistry
- Biomimetic Chemistry
- Biophysical Chemistry
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 (O2) and hydrogen peroxide (H2O2) 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.
Selected Publications —
Yilue Zhang, David S. Richards, Elizabeth N. Grotemeyer, Timothy A. Jackson, and Christian Schöneich, Near-UV and Visible Light Degradation of Iron (III)-Containing Citrate Buffer: Formation of Carbon Dioxide Radical Anion via Fragmentation of a Sterically Hindered Alkoxyl Radical. Molecular Pharmaceutics 2022 19 (11), 4026-4042 DOI: 10.1021/acs.molpharmaceut.2c00501
Nikola Kenjić, Kathleen M. Meneely, Daniel J. Wherritt, Melissa C. Denler, Timothy A. Jackson, Graham R. Moran, and Audrey L. Lamb, Evidence for the Chemical Mechanism of RibB (3,4-Dihydroxy-2-butanone 4-phosphate Synthase) of Riboflavin Biosynthesis. Journal of the American Chemical Society 2022 144 (28), 12769-12780 DOI: 10.1021/jacs.2c03376
Massie, A. A., Kostopoulos, N., Grotemeyer, E. N., Noel, J-M., Jackson, T. A., & Anxolabehere-Mallart, E. Electrochemical Formation and Reactivity of a Mn-Peroxo Complex Bearing an Amido N5 Ligand. ChemElectroChem 2022, 9, e202200112.
Singh, P.; Denler, M.C.; Mayfield, J.R.; Jackson, T.A.; Differences in chemoselectivity in olefin oxidation by a series of non-porphyrin manganese(iv)-oxo complexes†. Dalton Trans., 2022,51, 5938-5949
Zolnhofer, E. M.; Opalade, A. A.; Jackson, T. A.; Heinemann, F. W.; Meyer, K.; Krzystek, J.; Ozarowski, A.; Telser, J. Electronic Structure and Magnetic Properties of a Low-Spin CrII Complex: trans-[CrCl2(dmpe)2] (dmpe = 1,2-Bis(dimethylphosphino)ethane). Inorg. Chem.2021, 60, 17865-17877.
Zhu, H.D., T.A. Jackson, and B. Subramaniam, Highly Selective Isobutane Hydroxylation by Ozone in a Pressure-Tuned Biphasic Gas-Liquid Process. Acs Sustainable Chemistry & Engineering, 2021. 9(16): p. 5506-5512.
Singh, P., et al., Mechanistic insight into oxygen atom transfer reactions by mononuclear manganese(iv)-oxo adducts. Dalton Transactions, 2021. 50(10): p. 3577-3585.
Shi, H.H., et al., Selective ozone activation of phenanthrene in liquid CO2. Rsc Advances, 2021. 12(1): p. 626-630.
Opalade, A.A., et al., Characterization and chemical reactivity of room-temperature-stable Mn-III-alkylperoxo complexes. Chemical Science, 2021. 12(38): p. 13.
Opalade, A.A., et al., Controlling the Reactivity of a Metal-Hydroxo Adduct with a Hydrogen Bond. Journal of the American Chemical Society, 2021. 143(37): p. 15159-15175.
Opalade, A.A., E.N. Grotemeyer, and T.A. Jackson, Mimicking Elementary Reactions of Manganese Lipoxygenase Using Mn-hydroxo and Mn-alkylperoxo Complexes. Molecules, 2021. 26(23): p. 18.
Banerjee, A., et al., Probing the Mechanism for 2,4 '-Dihydroxyacetophenone Dioxygenase Using Biomimetic Iron Complexes. Inorganic Chemistry, 2021. 60(10): p. 7168-7179.
Mayfield, J.R., E.N. Grotemeyer, and T.A. Jackson, Concerted proton-electron transfer reactions of manganese-hydroxo and manganese-oxo complexes. Chemical Communications, 2020. 56(65): p. 9238-9255.
Kwon, Y.M., et al., Crystal Structure and C-H Bond-Cleaving Reactivity of a Mononuclear Co-IV-Dinitrate Complex. Journal of the American Chemical Society, 2020. 142(31): p. 13435-13441.
Awards & Honors —
Sutton Family Research Impact Award Recipient
Silver Anniversary Teaching Award, University of Kansas
NSF CAREER Award
ACS Young Investigator Award – Division of Inorganic Chemistry
Inorganic Chemistry Research Award, University of Wisconsin-Madison