Max Planck Research Group - EPR Spectroscopy of Metallorganic Compounds
Dr. George E. Cutsail III
|B.Sc. Chemistry (2010)||University of Maryland, Baltimore County, MD, USA|
|Ph.D. Chemistry (2014)||Northwestern University|
|Postdoc (2015-2019)||MPI CEC|
|Research Group Leader (seit 2019)||MPI CEC / Universität Duisburg-Essen|
Selected MPI CEC publications
- Helling, C., Wölper, C., Cutsail III, G.E., Haberhauer, G., Schulz, S. (2020). A mechanistic study on reactions of group 13 diyls LM with Cp*SbX2 ‐ From stibanyl radicals to antimony hydrides Chemistry – A European Journal https://doi.org/10.1002/chem.202001739
- Van Stappen, C., Decamps, L., Cutsail III, G.E., Bjornsson, R., Henthorn, J.T., Birrell, J.A., DeBeer, S. (2020). The Spectroscopy of Nitrogenases Chemical Reviews 120(12), 5005-5081. https://doi.org/10.1021/acs.chemrev.9b00650
- Helling, C., Cutsail III, G.E., Weinert, H., Wölper, C., Schulz, S. (2020). Ligand Effects on the Electronic Structure of Heteroleptic Antimony‐centered Radicals Angewandte Chemie International Edition 59(19), 7561-7568. https://doi.org/10.1002/anie.202000586
- Cutsail III, G.E., Blaesi, E.J., Pollock, C.J., Bollinger Jr, J.M., Krebs, C., DeBeer, S. (2020). High-resolution iron X-ray absorption spectroscopic and computational studies of non-heme diiron peroxo intermediates Journal of Inorganic Biochemistry 203, 110877. https://doi.org/10.1016/j.jinorgbio.2019.110877
- Liu, Y., Resch, S.G., Klawitter, I., Cutsail III, G.E., Demeshko, S., Dechert, S., Kühn, F.E., DeBeer, S., Meyer, F. (2020). An Adaptable N‐Heterocyclic Carbene Macrocycle Hosting Copper in three Oxidation States Angewandte Chemie International Edition 59(14), 5696-5705. https://doi.org/10.1002/anie.201912745
- McGale, J., Cutsail III, G.E., Joseph, C., Rose, M.J., DeBeer, S. (2019). Spectroscopic X-ray and Mössbauer Characterization of M6 and M5 Iron(Molybdenum)-Carbonyl Carbide Clusters: High Carbide-Iron Covalency Enhances Local Iron Site Electron Density Despite Cluster Oxidation Inorganic Chemistry 58(19), 12918-12932. https://doi.org/10.1021/acs.inorgchem.9b01870
- Cutsail III, G.E., Gagnon, N.L., Spaeth, A.D., Tolman, W.B., DeBeer, S. (2019). Valence‐to‐Core X ray Emission Spectroscopy as a Probe of O‐O Bond Activation in Cu2O2 complexes Angewandte Chemie International Edition 58(27), 9114-9119. https://doi.org/10.1002/anie.201903749
- Helling, C., Wölper, C., Schulte, Y., Cutsail III, G.E., Schulz, S. (2019). Synthesis of a Ga-Stabilized As-Centered Radical and a Gallastibene by Tailoring Group 15 Element–Carbon Bond Strengths Inorganic Chemistry 58(15), 10323-10332. doi.org/10.1021/acs.inorgchem.9b01519
- Cutsail III, G.E., Banerjee, R., Zhou, A., Que, L., Lipscomb, J.D., DeBeer, S. (2018). High-Resolution EXAFS Provides Evidence for a Longer Fe•••Fe Distance in the Q Intermediate of Methane Monooxygenase Journal of the American Chemical Society 140(48), 16807-16820. https://doi.org/10.1021/jacs.8b10313
- Galle, L.M., Cutsail III, G.E., Nischwitz, V., DeBeer, S., Span, I. (2018). Spectroscopic characterization of the Co-substituted C-terminal domain of rubredoxin-2 Biological Chemistry 399(7), 787-798. https://doi.org/10.1515/hsz-2018-0142
- Ganesamoorthy, C., Helling, C., Wolper, C., Frank, W., Bill, E., Cutsail III, G.E., Schulz, S. (2018). From stable Sb- and Bi-centered radicals to a compound with a Ga=Sb double bond Nature Communications 9, 87. https://doi.org/10.1038/s41467-017-02581-2
- Horitani, M., Offenbacher, A.R., Carr, C.A.M., Yu, T., Hoeke, V., Cutsail III, G.E., Hammes-Schiffer, S., Klinman, J.P., Hoffman, B.M. (2017). 13C ENDOR Spectroscopy of Lipoxygenase-Substrate Complexes Reveals the Structural Basis for C-H Activation by Tunneling Journal of the American Chemical Society 139(5), 1984-1997. https://doi.org/10.1021/jacs.6b11856
EPR Spectroscopy of Metallorganic Compounds
The Cutsail group employs inorganic spectroscopic techniques to elucidate structural and electronic information for (bio)inorganic systems. We primarily utilize Electron Paramagnetic Resonance (EPR) spectroscopy and advanced techniques such as Electron Nuclear Double Resonance (ENDOR) and Electron Spin Echo Envelope Modulation (ESEEM) spectroscopies. Selected systems are also studied by various X-ray absorption and emission spectroscopy.
Highly qualified and motivated scientists at all levels (Bachelors students to postdocs) who are interested in learning spectroscopy are always welcome to contact George Cutsail (george.cutsail(at)cec.mpg.de) about possible research opportunities.
The Cutsail research program aims to understand both the formation and cleavage of the O-O bond of dioxygen O2 by monocopper centers from two directions. We study both the cleavage of O-O bonds by monocopper monooxygenase proteins to form a powerful copper-oxygen oxidant intermediate. The electrochemical oxidation of water using nitrogen coordinated monocopper catalysts yields O2, affording a unique system to study the formation of O-O bonds facilitated by copper.
Techniques such as ENDOR and ESEEM allow for detailed insight into the copper center’s electronic structure. From these techniques, structures may be determined of coordinating ligands along with their covalency. Isotopic labelling (2H, 13C, 15N, 17O, etc.) further aids the selectivity of these studies. Furthermore, reaction mechanism can be studied by the rapid-freeze quenching of intermediates.
Approaching the chemistry of dioxygen and copper from these two directions allows for commonly proposed intermediates in each system to be independently characterized. The synergy between these two large projects help inform and further the spectroscopic characterization of copper-oxygen chemistry.
Main-Group Radical Characterization: Prof. Stephan Schulz (University of Duisburg-Essen)
Working with the research group of Prof. Stephan Schulz, we characterize novel Group 15 radical stabilized by electropositive ligands. The variety of As, Sb, and Bi centered radicals exhibit intriguing EPR spectroscopic properties with complex resolved super-hyperfine interactions from the various NMR-active nuclei of these complexes. Multi-frequency EPR spectroscopy allows for high-precision and accuracy of all EPR parameters.
- C Helling, C Wölper, Y Schulte, GE Cutsail III, S Schulz*, "Synthesis of a Ga-Stabilized As-Centered Radical and a Gallastibene by Tailoring Group 15 Element-Carbon Bond Strengths", Inorg. Chem., 2019, 58, 10323-10332 https://dx.doi.org/10.1021/acs.inorgchem.9b01519
- C Ganesamoorthy, C Helling, C Wölper, W Frank, E Bill, GE Cutsail III*, S Schulz*, "From Stable Sb- and Bi-centered Radicals to a Compound with a Ga=Sb Double Bond", Nature Comm. 2018, 9, 87 https://doi.org/10.1038/s41467-017-02581-2