SELECTIVE FUNCTIONALIZATION OF HYDROCARBONS
Photo-driven, selective, partial oxidation of light alkanes: What started as a thermal investigation into the conversion of light alkanes to trifluoromethyl-esterified products by iodate and chloride salts in trifluoroacetic acid was found to also be facilitated under photo-driven conditions, and notably, with higher yields. The photochemical reactivity of light alkanes has since become a focus of research for this project, moving from studying inorganic salts to transition metal complexes as photocatalysts. Currently, efforts are underway to explore systems that can successfully perform this photo-driven chemistry with light alkanes in milder solvents (other than trifluoroacetic acid) in which the alkyl ester products are protected from over-oxidation.
Transition metal catalyzed functionalization of hydrocarbons: Transition metal catalyzed C–H functionalization of inactivated hydrocarbons remains a significant challenge. Our group focuses on the design of new transition metal catalysts for C–H activation in combination with functionalization reaction sequences. Through detailed mechanistic understanding, we seek to tune ligands and catalyst structure to optimize rates and selectivity.
Relevant Publications
1. "Partial Oxidation of Methane Enabled by Decatungstate Photocatalysis Coupled to Free Radical Chemistry" Musgrave, C. B., III, Olsen, K., Liebov, N. S., Groves, J. T., Goddard, W. A., III, Gunnoe, T. B. ACS Catal. 2023, 6382-6395. DOI: 10.1021/acscatal.3c00750
2. "Cu(II) Carboxylate Arene C–H Functionalization: Tuning for Non-Radical Pathways" Kong, F., Chen, S., Chen, J., Liu, C., Zhu, W., Dickie, D. A., Zhang, S., Ess, D.*, Gunnoe, T. B.* Sci. Adv. 2022, 8, 1-14. DOI: 10.1126/sciadv.add1594
3. "Manganese Catalyzed Partial Oxidation of Light Alkanes" Coutard, N. Musgrave III, C. B., Moon, J., Liebov, N. S., Nielsen, R. M., Goldberg, J. M., Li, M., Jia, X., Lee, S., Dickie, D. A., Schinski, W. L. Wu, Z., Groves, J. T., Goddard III, W. A.*, Gunnoe, T. B.* ACS Catal. 2022, 12(9), 5356–5370 DOI: 10.1021/acscatal.2c00982
4. "Aerobic Partial Oxidation of Alkanes using Photo-driven Iron Catalysis" Coutard, N., Goldberg, J. M., Valle, H. U., Cau, Y., Jia, X., Jeffrey, P. D., Gunnoe, T. B.*, Groves, J. T.* Inorg. Chem. 2022, 61, 759-766. DOI: 10.1021/acs.inorgchem.1c03086 (paper selected as a Feature Article by Inorg. Chem.)
5. "Reductive C–C coupling from Molecular Au(I) Hydrocarbyl Complexes: A Mechanistic Study" Mirando-Pizarro, J., Luo, Z., Moreno, J. J., Dickie, D. A., Campos, J.*, Gunnoe, T. B.* J. Am. Chem. Soc. 2021, 143, 2509-2522. DOI: 10.1021/jacs.0c11296
6. "Functionalization of RhIII–Me Bonds: Use of "Capping Arene" Ligands to Facilitate Me–X Reductive Elimination" Gu, S., Chen, J. Musgrave III, C. B., Gehman, Z. M., Habgood, L. G., Jia, X., Dickie, D. A., Goddard III*, W. A., Gunnoe*, T. B. Organometallics 2021, 40, 1889-1906. DOI: 10.1021/acs.organomet.1c00223 (paper selected as cover issue, (selected as a cover feature, listed as a "Top 3 most read" manuscript for the month and "Super Seven" as the fifth most read manuscript for the 2021 year)
7. "Effects of Additives on Catalytic Arene C–H Activation: Study of Rh Catalysts Supported by Bis-phosphine Pincer Ligands" Kong, F., Gu, S., Liu, C., Dickie, D. A., Zhang, S., Gunnoe, T. B.* Organometallics 2020, 39, 3918-3935. DOI: 10.1021/acs.organomet.0c00623
8. "Effects of Additives on Catalytic Arene C–H Activation: Study of Rh Catalysts Supported by Bis-phosphine Pincer Ligands" Kong, F., Gu, S., Liu, C., Dickie, D. A., Zhang, S., Gunnoe, T. B.* Organometallics 2020, 39, 3918-3935. DOI: 10.1021/acs.organomet.0c00623
9. "Mechanism of Hydrocarbon Functionalization by an Iodate/Chloride System: The Role of Ester Protection" Schwartz, N. A., Boaz, N. C., Kalman, S. E., Zhuang, T., Goldberg, J. M., Fu, R., Nielsen, R. J., Goddard III, W. A., Groves, J. T.*, Gunnoe, T. B.,* ACS Catalysis 2018 8, 3138-3149. DOI: 10.1021/acscatal.7b04397