Article
Chemistry, Physical
Lin Gong, Ji Sun, Yousong Liu, Guangcheng Yang
Summary: This study demonstrates the efficient use of solar energy to drive CO2 cycloaddition conversion under mild reaction conditions using a Zn single-atom-loaded N-doped carbon catalyst. The catalyst shows high catalytic activity with almost complete CO2 conversion yields, providing unprecedented findings for the future design and application of single-atom catalysts in photoinduced CO2 cycloaddition catalysis or other catalytic reactions.
JOURNAL OF MATERIALS CHEMISTRY A
(2021)
Article
Chemistry, Organic
Wenqin Qiu, Feng Jin, Yanhong Hao, Xiaoguang Bao, Dan Yuan, Yingming Yao
Summary: A non-metal catalyzed coupling of epoxy amines and CO2 was achieved using readily available tertiary amines, leading to the selective synthesis of oxazolidinones. This strategy allows for the production of various oxazolidinones under mild conditions and has been successfully applied to the synthesis of the chiral antibiotic drug linezolid.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Thitirat Piyawongsiri, Nattiya Laiwattanapaisarn, Arnut Virachotikul, Phongnarin Chumsaeng, Khamphee Phomphrai
Summary: This study reports a potential route for synthesizing cyclic carbonates through the coupling reaction of epoxides with carbon dioxide. The researchers discovered that a complex containing indium metal and tert-butyl substituents exhibited the highest catalytic activity and selectivity under solvent-free conditions.
Article
Chemistry, Multidisciplinary
Kori A. Andrea, Mikhailey D. Wheeler, Francesca M. Kerton
Summary: Triphenylborane catalyzes the polymerization of anhydrides and epoxides, while tris(pentafluorophenyl)borane can selectively depolymerize the carbonate block of the polymer to yield cyclic carbonates, allowing for chemical repurposing of the polymer.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Inorganic & Nuclear
Bianca K. Munoz, Monica Viciano, Cyril Godard, Sergio Castillon, Monica Garcia-Ruiz, Ma Dolores Blanco Gonzalez, Carmen Claver
Summary: The paper discusses the use of metal complexes as catalysts in the synthesis of propylene carbonate from carbon dioxide and propylene oxide. Iron and manganese complexes showed significantly higher activities compared to new cobalt complexes. By optimizing the conditions, a TOF of 1600 h-1 was achieved with the manganese (II) complex 2.
INORGANICA CHIMICA ACTA
(2021)
Article
Biochemistry & Molecular Biology
Jose J. Delgado-Marin, Iris Martin-Garcia, David Villalgordo-Hernandez, Francisco Alonso, Enrique Ramos-Fernandez, Javier Narciso
Summary: One potential way to utilize CO2 is to react it with organic epoxides to produce cyclic carbonates. However, no efficient and selective heterogeneous catalyst has been discovered yet. In this study, cobalt and zinc-based zeolitic imidazole frameworks (ZIFs) were explored as catalysts for this reaction. Modified ZIF-8 and ZIF-67 catalysts were prepared and showed excellent catalytic performance in the cycloaddition of CO2 with epichlorohydrin. Notably, these reactions occurred under mild conditions without the need for co-catalysts.
Article
Chemistry, Multidisciplinary
Jijun Xie, Fei Chen, Min Li, Ning Liu
Summary: A new family of [ONSN]-type chromium complexes with hybrid coordination site (O, N, S) has been developed for the coupling of epoxides with CO2. The catalytic system shows high activity for the cycloaddition of various epoxides with CO2. By switching the catalyst system and adjusting reaction conditions, selective synthesis of poly(cyclohexene carbonate) can be achieved.
JOURNAL OF CO2 UTILIZATION
(2022)
Article
Chemistry, Physical
Masatoshi Mihara, Shuichi Nakao, Takeo Nakai, Takumi Mizuno
Summary: The development of an effective catalytic system for the cycloaddition of carbon dioxide to epoxides is crucial. In this study, a mixture of zinc iodide, metal chlorides, and strong organic bases was found to be a useful catalytic system that works at room temperature and atmospheric pressure. The most efficient combination produced styrene carbonate (95%) and propylene carbonate, showing that this method is a powerful tool for utilizing CO2 in the production of valuable chemicals.
Article
Chemistry, Multidisciplinary
Irene Contento, David Hermann Lamparelli, Antonio Buonerba, Alfonso Grassi, Carmine Capacchione
Summary: The newly developed family of chromium complexes can be used for the cycloaddition of epoxides with CO2, showing high activity and selectivity for the synthesis of cyclic carbonates.
JOURNAL OF CO2 UTILIZATION
(2022)
Article
Engineering, Chemical
Dong-Hui Lan, Kun Chen, Heng-Jun Zhu, Jing Shen, Shui-Sheng Wu, Chak-Tong Au, Bing Yi, ShuangFeng Yin
Summary: By synthesizing Lewis acid-base hexamethylenetetramine complexes with multisynergetic effects, the goal of synthesizing cyclic carbonates without solvents or cocatalysts under mild conditions was successfully achieved. The experimental results indicate that the Lewis acidity of the metal and the nucleophilicity of the anions play crucial roles in the catalytic performance.
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
(2022)
Review
Chemistry, Multidisciplinary
Feng Han, Heng Li, Hongfeng Zhuang, Qin Hou, Qingfeng Yang, Bing Zhang, Chengxia Miao
Summary: The conversion of CO2 to high value-added chemicals is urgent due to the rise in carbon dioxide emissions and its importance as a renewable chlorine source. Developing efficient catalytic systems for the synthesis of cyclic carbonates is crucial for practical applications. The review article discusses the comprehensive developments in catalytic systems, classified into transition metal and transition-metal-free ones, with a focus on single- or multi-component catalytic systems. Transition-metal-free systems mainly involve quaternary ammonium salts or ionic liquids, while multi-component catalytic systems contain noble and nonnoble metals along with quaternary ammonium salts for catalysis. Insights from the intermediates in the mechanisms are presented for designing multifunctional catalysts and developing new transformation strategies.
JOURNAL OF CO2 UTILIZATION
(2021)
Article
Chemistry, Physical
Angela Mesias-Salazar, Yersica Rios Yepes, Javier Martinez, Rene S. Rojas
Summary: A series of alkyl aluminum adducts supported by benzodiimidazole-diylidene ligands were synthesized and used as catalysts for the efficient formation of cyclic carbonates. Among them, adduct 1 showed the highest efficiency in synthesizing various monosubstituted cyclic carbonates with excellent conversions and yields under specific conditions.
Article
Chemistry, Inorganic & Nuclear
Lamia A. Siddig, Reem H. Alzard, Abdalla S. Abdelhamid, Tholkappiyan Ramachandran, Ha L. Nguyen, Alejandro Perez Paz, Ahmed Alzamly
Summary: In this study, a novel cobalt hydrogen-bonded organic framework material was synthesized through a simple and low-cost method. The material showed high thermal and chemical stabilities and exhibited excellent photocatalytic activity under visible light irradiation. The cycloaddition reaction of CO2 to variable epoxides catalyzed by the material resulted in high yields of corresponding cyclic carbonates.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Yasunori Toda, Ryota Shiokawa, Masaya Iwasaki, Daisuke Yamaguchi, Keisuke Kawamura, Kimiya Sukegawa, Hiroyuki Suga
Summary: This study presents an efficient method for the regioselective synthesis of beta-amino alcohol derivatives, including enantioenriched ones, by a tetraarylphosphonium salt-catalyzed coupling reaction of epoxides with trichloroacetonitrile.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Haonan Lin, Cheng-Hua Deng, Xiaohang Qiu, Xiao Liu, Jian-Gong Ma, Peng Cheng
Summary: Three new manganese-based metal-organic frameworks have been synthesized with modified structures for improved catalytic activity in the reaction of CO2 and epoxides towards cyclic carbonates. The structures of the Mn-MOFs are controlled by changing the anions of the manganese salts, and the catalytic activities are optimized under mild conditions.
CRYSTAL GROWTH & DESIGN
(2021)
Article
Chemistry, Multidisciplinary
Trung Le, Hao Nguyen, Lisa M. Perez, Donald J. Darensbourg, Marcetta Y. Darensbourg
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2020)
Article
Chemistry, Inorganic & Nuclear
Gulzar A. Bhat, Ahmed Z. Rashad, Tucker M. Folsom, Donald J. Darensbourg
Article
Polymer Science
Gulzar A. Bhat, Marcetta Y. Darensbourg, Donald J. Darensbourg
Summary: The synthesis of poly(propylene carbonate) with 100% C-13-labeled carbonate carbons has been reported, where the nu(CO3) vibration is lowered by 45 cm(-1), allowing for the observation of nu(NO) stretching motions in incorporated dinitrosyl iron complexes.
Article
Chemistry, Multidisciplinary
Tian-Jun Yue, Bai-Hao Ren, Wen-Jian Zhang, Xiao-Bing Lu, Wei-Min Ren, Donald J. Darensbourg
Summary: A synthetic strategy was presented for enhancing the optical properties of CO2-based polycarbonates by modifying the polymer's topological structure, resulting in terpolymers with tunable carbonate linkages and improved optical properties. This approach offers a promising method for developing polymeric materials with enhanced optical properties while maintaining thermal stability.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Gulzar A. Bhat, Ahmed Z. Rashad, Xiaozhou Ji, Manuel Quiroz, Lei Fang, Donald J. Darensbourg
Summary: In this study, TEMPO-appended polymonothiocarbonates were synthesized through ring-opening copolymerization under ambient conditions. Both atactic and isotactic versions of the polymer were prepared, with the isotactic form showing significantly higher conductivity attributed to its well-defined stereochemistry and regulated charge transport pathway compared to the atactic counterpart.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Mani Sengoden, Gulzar A. Bhat, Donald J. Darensbourg
Summary: Polymers obtained from renewable monomers have attracted attention for their ability to address environmental issues and depletion of fossil fuels. In this study, a renewable eugenol-based epoxide was synthesized and its reactions with CO2, COS, and CS2 were examined. It was found that eugenol epoxide preferentially formed cyclic products with CO2 and CS2, while reacting with COS resulted in the regioselective formation of polymonothiocarbonate polymers at room temperature. The molecular structures of the renewable monomers and their cyclic products were determined using single crystal X-ray diffraction studies. Thermal gravimetric analysis and differential scanning calorimetry revealed that the polymonothiocarbonate polymers were stable up to 200 degrees C and had high glass transition temperatures.
Article
Chemistry, Inorganic & Nuclear
Zachary M. Martinez, Tucker M. Folsom, Yicheng Tong, Ashley K. Archambeau, Donald J. Darensbourg, Michael B. Hall, Cynthia B. Powell, Gregory L. Powell
Summary: The mechanism of CO substitution reaction involving diosmium carbonyl sawhorse complex was studied experimentally and theoretically, revealing a dissociative interchange mechanism. Kinetic measurements and stability studies were in agreement with each other, explaining the unexpected combination of kinetics and stability characteristics observed in the reaction.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Fang-Yu Ren, Kaihong Chen, Li-Qi Qiu, Jin-Mei Chen, Donald J. Darensbourg, Liang-Nian He
Summary: A triblock amphiphilic polymer derived from the copolymerization of CO2 and epoxides is able to efficiently catalyze the visible-light-driven reduction of CO2 to CO. The polymer forms spherical micelles in water, where the metal catalyst is sequestered. The amphiphilic polycarbonate micelle rhenium catalyst shows enhanced catalytic activity and selectivity compared to the corresponding molecular rhenium catalyst in organic solvent, while also suppressing the generation of H-2.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Peiran Wei, Gulzar A. Bhat, Ciera E. Cipriani, Hamza Mohammad, Krista Schoonover, Emily B. Pentzer, Donald J. Darensbourg
Summary: This study reports on the facile synthesis and 3D printing of triblock copolymers that can be covalently modified. Thixotropic inks suitable for direct ink write printing were formulated by dissolving the block copolymers in organic solvent and dispersing NaCl particles. Printed structures with surfaces that could be modified and objects with high solvent resistance and selective degradability were achieved.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Polymer Science
Mani Sengoden, Gulzar A. Bhat, Donald J. Darensbourg
Summary: In recent years, chemists worldwide have made significant progress in synthesizing sustainable polymers from natural product-based building blocks. This shift is driven by the environmental impact of non-biodegradable oil-based polymers and the need to utilize renewable feedstocks. This study presents the synthesis of novel terpolymer using a well-defined catalyst system and investigates the mechanistic details of the polymerization reactions. The resulting terpolymers show increased thermal stability with higher proportions of the renewable building block.
Review
Chemistry, Multidisciplinary
Peiran Wei, Gulzar A. Bhat, Donald J. Darensbourg
Summary: This paper presents a concise review of recent progress in processing techniques for aliphatic polycarbonates, including controlled self-assembly, electrospinning, additive manufacturing, and others. The aim is to provide researchers with an enriched toolbox for selecting the most suitable technique for their materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Mani Sengoden, Gulzar A. Bhat, Donald J. Darensbourg
Summary: Recent years have seen significant research efforts in the development of metal-free organocatalysts for coupling reactions of CO2 and epoxides. In this study, a series of boron-phosphonium organocatalysts were synthesized and characterized for catalyzing these reactions. The catalysts exhibited high selectivity and were found to be less hygroscopic compared to metal-based catalysts. They successfully facilitated the copolymerization of CO2 and epoxides to form polycarbonates.
Review
Chemistry, Multidisciplinary
Gulzar A. Bhat, Donald J. Darensbourg
Summary: Sustainability requires the reuse of carbon sources from CO2 emissions, making carbon capture and utilization essential. Coupling of oxiranes (epoxides) with CO2 can generate cyclic carbonates and polymeric materials, providing a potential solution. It is important to use epoxides derived from renewable resources for a sustainable process.
Article
Polymer Science
David K. Tran, Ahmed Z. Rashad, Donald J. Darensbourg, Karen L. Wooley
Summary: The synthetic transformation of d-xylose into a four-membered cyclic ether enables reactions with carbon dioxide to produce linear polycarbonates through either one-step ring-opening copolymerisation (ROCOP) directly or sequential isolation of a preformed six-membered cyclic carbonate followed by ring-opening polymerisation (ROP).
Review
Chemistry, Multidisciplinary
Yao-Yao Zhang, Guang-Peng Wu, Donald J. Darensbourg
TRENDS IN CHEMISTRY
(2020)