Max Planck Research Group - EPR Spectroscopy of Metallorganic Compounds

Dr. George E. Cutsail III

Vita

B.Sc. Chemistry (2010) University of Maryland, Baltimore County, MD, USA
Ph.D. Chemistry (2014) Northwestern University
Postdoc (2015-2019) MPI CEC
Forschungsgruppenleiter (seit 2019) MPI CEC / Universität Duisburg-Essen
Publications

Full publications list | ORCID | Google Scholar Profile

Selected MPI CEC publications

  • Hau, J.-L., Kaltwasser, S., Muras, V., Casutt, M. S., Vohl, G., Claussen, B., Steffen, W., Leitner, A., Bill, E., Cutsail, G. E., DeBeer, S., Vonck, J., Steuber, J., Fritz, G. (2023). Conformational coupling of redox-driven Na+-translocation in <i>Vibrio cholerae</i> NADH:quinone oxidoreductase. Nature Structural & Molecular Biology, (xx), 1-31. doi:10.1038/s41594-023-01099-0.
  • Sharma, M. K., Weinert, H. M., Li, B., Wölper, C., Henthorn, J. T., Cutsail III, G. E., Haberhauer, G., Schulz, S. (2023). Syntheses and Structures of 5-Membered Heterocycles Featuring 1,2-Diphospha-1,3-Butadiene and Its Radical Anion. Angewandte Chemie, International Edition in English, (62): e202309466, pp. 1-6. doi:10.1002/anie.202309466.
  • Liu, Y., Chatterjee, S., Cutsail III, G. E., Peredkov, S., Gupta, S. K., Dechert, S., DeBeer, S., Meyer, F. (2023). Cu4S Cluster in "0-Hole" and "1-Hole" States: Geometric and Electronic Structure Variations for the Active Cu-Z* Site of N2O Reductase. Journal of the American Chemical Society, 145(33), 18477-18486. doi:10.1021/jacs.3c04893.
  • Cutsail III, G., Schott-Verdugo, S., Müller, L., DeBeer, S., Groth, G.,  Gohlke, H. (2022). Spectroscopic and QM/MM studies of the Cu(I) binding site of the plant ethylene receptor ETR1. BIOPHYSICAL JOURNAL, 121(20), 3862-3873. doi:10.1016/j.bpj.2022.09.007.
  • Cutsail III, G. E., Banerjee, R., Rice, D. B., Stepanic, O. M., Lipscomb, J. D.,  DeBeer, S. (2022). Determination of the iron(IV) local spin states of the Q intermediate of soluble methane monooxygenase by K beta X-ray emission spectroscopy. Journal of Biological Inorganic Chemistry, (27), 573-582. doi:10.1007/s00775-022-01953-4.
  • Haak, J., Krüger, J., Abrosimov, N. V., Helling, C., Schulz, S.,  Cutsail III, G. E. (2022). X-Band Parallel-Mode and Multifrequency Electron Paramagnetic Resonance Spectroscopy of S=1/2 Bismuth Centers. Inorganic Chemistry, 61(29), 11173-11181. doi:10.1021/acs.inorgchem.2c01141.
  • Helling, C., Haak, J., Wölper, C., Cutsail III, G. E.,  Schulz, S. (2022). Sequential Reduction of Borylstibane to an ElectronicallyNonsymmetric Diboryldistibene Radical Anion br. Inorganic Chemistry, 61(12), 5124-5132. doi:10.1021/acs.inorgchem.2c00251.
  • Cutsail III, G. E.,  DeBeer, S. (2022). Challenges and Opportunities for Applications of Advanced X-ray Spectroscopy in Catalysis Research. ACS Catalysis, 12(10), 5864-5886. doi:10.1021/acscatal.2c01016.
  • Li, B., Geoghegan, B. L., Weinert, H. M., Wolper, C., Cutsail III, G. E.,  Schulz, S. (2022). Synthesis and redox activity of carbene-coordinated group 13 metal radicals. Chemical Communications, 58(27), 4372-4375. doi:10.1039/d2cc00216g.
  • Henthorn, J. T., Cutsail III, G. E., Weyhermüller, T., DeBeer, S. (2022). Stabilization of intermediate spin states in mixed-valent diiron dichalcogenide complexes. Nature Chemistry, (14), 328-333. doi:10.1038/s41557-021-00853-5.
  • Geoghegan, B. L., Liu, Y., Peredkov, S., Dechert, S., Meyer, F., DeBeer, S., Cutsail III, G. E. (2022). Combining Valence-to-Core X-ray Emission and Cu K-edge X-ray Absorption Spectroscopies to Experimentally Assess Oxidation State in Organometallic Cu(I)/(II)/(III) Complexes. Journal of the American Chemical Society, 144(6), 2520-2534. doi:10.1021/jacs.1c09505.
  • Levin, N., Casadevall, C., Cutsail III, G. E., Lloret-Fillol, J., DeBeer, S.,  Rüdiger, O. (2022) XAS and EPR in Situ Observation of Ru(V) Oxo Intermediate in a Ru Water Oxidation Complex**. ChemElectroChem, e202101271, pp. 1-4. doi:10.1002/celc.202101271.
  • Cutsail III, G. E., Ross, M. O., Rosenzweig, A. C., DeBeer, S. (2021). Towards a unified understanding of the copper sites in particulate methane monooxygenase: an X-ray absorption spectroscopic investigation dagger. Chemical Science, (12), 6194-6209. doi:10.1039/d1sc00676b.
  • Li, B., Geoghegan, B. L., Wölper, C., Cutsail III, G. E.,  Schulz, S. (2021). Redox Activity of Noninnocent 2,2 '-Bipyridine in Zinc Complexes: An Experimental and Theoretical Study. ACS Omega, 6(28), 18325-18332. doi:10.1021/acsomega.1c02201.
  • Schulte, Y., Geoghegan, B. L., Helling, C., Wölper, C., Haberhauer, G., Cutsail III, G. E., Schulz, S. (2021). Observation of Discrete Valence Tautomers in Crystalline Cyclopentadienyl Radicals. Journal of the American Chemical Society, 143(32), 12658-12664. doi:10.1021/jacs.1c05210.
  • Weinert, H. M., Wölper, C., Haak, J., Cutsail, G. E., Schulz, S. (2021). Synthesis, structure and bonding nature of heavy dipnictene radical anions. Chemical Science, (12),14024-14032 doi:10.1039/d1sc04230k.
  • Rosenbach, H., Walla, E., Cutsail III, G. E., Birrell, J. A., Pascual-Ortiz, M., DeBeer, S., Fleig, U., Span, I. (2021). The Asp1 pyrophosphatase from S. pombe hosts a [2Fe-2S]2+ cluster in vivo. Journal of Biological Inorganic Chemistry. https://doi:10.1007/s00775-020-01840-w.
  • Duan, P.-C., Schulz, R.A., Römer, A., Van Kuiken, B.E., Dechert, S., Demeshko, S., Cutsail III, G.E., DeBeer, S., Mata, R.A., Meyer, F. (2021). Ligand Protonation Triggers H2 Release from a Dinickel Dihydride Complex to Give a Doubly “T”‐Shaped Dinickel(I) Metallodiradical Angewandte Chemie International Edition 60,1891–1896 https://doi.org/10.1002/anie.202011494
  • Cutsail III, G.E. (2020). Applications of electron paramagnetic resonance spectroscopy to heavy main-group radicals Dalton Transactions 49(35), 12128-12135. https://doi.org/10.1039/D0DT02436H
  • 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 26(59), 13390-13399. 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. https://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
Group members

Postdocs

Dr. Aleksa Radovic

PhD students

Julia Haak

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.

[Translate to EN:] Figure adapted from: Helling, C., et al. https://dx.doi.org/10.1021/acs.inorgchem.9b01519
  • 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