The fundamentally interesting and challenging chemistry associated with carbon dioxide, coupled with its high potential as a source of chemical carbon, provides adequate justification for comprehensive investigations in this area. In our research program we have attempted to establish a clearer mechanistic view of carbon-hydrogen, carbon-carbon, and carbon-oxygen bond forming processes resulting from carbon dioxide insertion into M-H, M-C, and M-O bonds.
Relevant to the latter process our research has addressed the utilization of carbon dioxide in the development of improved synthetic routes for the production of polycarbonates. The hazardous and expensive production process currently in place industrially for these materials involves the interfacial polycondensation of phosgene and diols, accentuates the need for these studies. Although we and others have made significant advances in the synthesis of these useful thermoplastics from carbon dioxide and epoxides much of the fundamental knowledge concerning the reaction kinetics of these processes is lacking, due in part to the practical challenges associated with sampling and analyzing systems at elevated temperatures and pressures. This information is needed for making this process applicable to the synthesis of a variety of copolymers possessing a range of properties and uses. Our studies are examining in detail the mechanistic aspects of metal catalyzed carbon dioxide/epoxide coupling reactions employing in situ spectroscopy methods. For this purpose Fourier-transform infrared attenuated total refluctance (FTIR/ATR) spectroscopy is being utilized. Other related investigations involve the development of structural and reactivity models for the industrially prevalent double metal cyanide catalysts(DMC) used in polyethers and polycarbonate synthesis from epoxides or CO2/epoxides, respectively.
- Yue, T., Ren, B., Zhang, W., Lu, X., Ren, W., & Darensbourg, D. J. (2020). Randomly Distributed Sulfur Atoms in the Main Chains of CO2‐Based Polycarbonates: Enhanced Optical Properties. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION. 60(8), 4315-4321.
- Zhang, Y., Wu, G., & Darensbourg, D. J. (2020). CO2-Based Block Copolymers: Present and Future Designs. Trends in Chemistry. 2(8), 750-763.
- Bhat, G. A., Darensbourg, M. Y., & Darensbourg, D. J. (2020). Copolymerization of propylene oxide and 13CO2 to afford completely alternating regioregular 13C-labeled Poly(propylene carbonate). Polymer Journal. 53(1), 215-218.
- Yue, T., Bhat, G. A., Zhang, W., Ren, W., Lu, X., & Darensbourg, D. J. (2020). Facile Synthesis of Well‐Defined Branched Sulfur‐Containing Copolymers: One‐Pot Copolymerization of Carbonyl Sulfide and Epoxide. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION. 59(32), 13633-13637.
- Bhat, G. A., Rashad, A. Z., & Darensbourg, D. J. (2020). Synthesis of terpyridine-containing polycarbonates with post polymerization providing water-soluble and micellar polymers and their metal complexes. Polymer Chemistry. 11(29), 4699-4705.
- Darensbourg, D. J. (2011). Salen Metal Complexes as Catalysts for the Synthesis of Polycarbonates from Cyclic Ethers and Carbon Dioxide. Advances in Polymer Science. Synthetic Biodegradable Polymers. (pp. 1-27). Springer Berlin Heidelberg.
- Darensbourg, D. J., Moncada, A. I., & Wilson, S. J. (2011). Ring‐Opening Polymerization of Renewable Six‐Membered Cyclic Carbonates. Monomer Synthesis and Catalysis. Green Polymerization Methods. (pp. 163-200). Wiley-VCH Verlag GmbH & Co. KGaA.
- Darensbourg, D. J., Andreatta, J. R., & Moncada, A. I. (2010). Polymers from Carbon Dioxide: Polycarbonates, Polythiocarbonates, and Polyurethanes. Carbon Dioxide as Chemical Feedstock. (pp. 213-248). Wiley-VCH Verlag GmbH & Co. KGaA.
- Joo, F., Kovacs, J., Katho, A., Benyei, A. C., Decuir, T., Darensbourg, D. J., Miedaner, A., & Dubois, D. L. (1998). (Meta-Sulfonatophenyl)Diphenylphosphine,Sodium Salt and Its Complexes with Rhodium(I), Ruthenium(II), Iridium(I). INORGANIC SYNTHESES. (pp. 1-8).
- Darensbourg, D. (2018). The synthesis of CO2-based polycarbonates with functionalities. ACS National Meeting Book of Abstracts. 256,
- Darensbourg, D. J. (2014). Current status of copolymerization reactions of carbon dioxide and epoxides. ACS National Meeting Book of Abstracts. 248,
- Cedeno-Alicea, J. A., Kyran, S. J., & Darensbourg, D. J. (2014). Aminophosphine tungsten carbonyls as potential scaffolds for CO2/olefin coupling. ACS National Meeting Book of Abstracts. 247,
- Pulukkody, R., Kyran, S. J., Bethel, R. D., Hsieh, C. H., Hall, M. B., Darensbourg, D. J., & Darensbourg, M. Y. (2014). Carbon Monoxide Induced Reductive Elimination of Disulfide in an N-Heterocyclic Carbene (NHC)/Thiolate Dinitrosyl Iron Complex (DNIC). JBIC Journal of Biological Inorganic Chemistry. 19, S419-S419.
- Chung, W., & Darensbourg, D. J. (2014). Copolymerization of cyclopentene oxide with CO2 utilizing bifunctional cobalt(III)- and chromium(III)-salen catalysts. ACS National Meeting Book of Abstracts. 247,
- Wang, Yanyan (2018-08). Development of Functional Polycarbonate Materials from Metal-catalyzed Copolymerization of Epoxides and CO2. (Doctoral Dissertation)
- Kyran, Samuel John (2015-12). Activation of Carbon Oxides: Chemical Reactions and Transformations Facilitated by Groups 6, 7, & 8 Metal Complexes. (Doctoral Dissertation)
- Chung, Wan-Chun (2015-12). Cobalt and Chromium Salen Complexes Catalyzed Copolymerization of CO2 and Epoxides: The Scope of Epoxides. (Doctoral Dissertation)
- Yeung, Andrew D (2014-12). Conversion of CO2 to Polycarbonates and Other Materials: Insights through Computational Chemistry. (Doctoral Dissertation)
- Wilson, Stephanie Jo (2013-08). Coupling of CO_(2) and CS_(2) with Novel Oxiranes: Polycarbonate vs. (Cyclic Carbonate Production. Doctoral Dissertation)