Vejleder: Christine McKenzie
Projektbeskrivelse
Inspired by diverse metalloenzymes found in Nature we aim at the discovery of simpler and robust complexes based on sustainable earth-abundant metal ions (e.g. Fe), which mimic their reactivity in catalysing regio- and stereo-selective atom-economic reactions. A particular focus is coupled C-H and O2 activation. The aim is that O2 directly from air might be employed as the terminal oxidant. A large proportion of chemical waste is from the production of pharmaceuticals is derived from oxidation reactions and this biomimetic approach promises to alleviate this.
Specific projects:
- The preparation of new ligands and for iron and manganese complexes which will be tested as catalysts[1,2,3] and electrocatalysts.[4]
- New crystalline metal-organic polymeric materials which chemisorb gases for use in devices for gas processing e.g. for the medical delivery of O2[5], and the sorption and conversion of toxic gases like NO,[6] CO.
This research impacts into areas as diverse as greener methods for organic synthesis, renewable energy production (Artificial Photosynthesis) and water remediation from organic pollutants like pesticides.
Work involves synthesis, spectroscopy, analytical chemistry and X-ray diffraction and collaboration with national and international groups expert in computational chemistry and spectroscopic methods not available at SDU.
[1] C. Wegeberg, V. M. Fernández-Alvarez, A. de Aguirre, C. Frandsen, W. R. Browne, F. Maseras and C. J. McKenzie, Photoinduced O2-dependent Stepwise Oxidative Deglycination of a Non-Heme Iron(III) Complex, J. Am. Chem. Soc., 2018, 140, 14150–14160.
[2] C. Deville, S. K. Padamati, Jonas Sundberg, V. McKee, W. R. Browne and C. J. McKenzie, O2 Activation and Double C-H Oxidation by a Mononuclear Manganese(II) Complex, Angew., Chem., Int. Ed. 2016, 55, 545-549.
[3] C. Wegeberg, W. R. Browne and C. J. McKenzie, Catalytic Alkyl Hydroperoxide and Acyl Hydroperoxide Disproportionation by a Non-heme Iron Complex, ACS Catalysis, 2018, 8, 9980-9991.
[4] D. P. de Sousa, C. J. Miller, Y. Chang, T. D. Waite, C. J. McKenzie, Electrochemically Generated Cis-Carboxylate Coordinated Iron(IV)-Oxo Acid-Base Congeners as Promiscuous Oxidants of Water Pollutants, Inorganic Chemistry, 2017, 56, 14936–14947.
[5] J. Sundberg, L. J. Cameron, P.D. Southon, C. J. Kepert and C. J. McKenzie, Oxygen Chemisorption/Desorption in a Reversible Single-Crystal-To-Single-Crystal Transformation, Chemical Science, 2014, 5, 4017–4025.
[6] M. Sondrup Møller, A. Haag, V. McKee, and C. J. McKenzie, NO Sorption, In-crystal Nitrite and Nitrate Production with Arylamine Oxidation in Gas-Solid Single Crystal to Single Crystal Reactions, Chemical Communications, 2019, 55, 10551-10554.