Article
Chemistry, Multidisciplinary
Josep Mas-Rosello, Christopher J. Cope, Eric Tan, Benjamin Pinson, Alan Robinson, Tomas Smejkal, Nicolai Cramer
Summary: Cyclometalated cyclopentadienyl iridium(III) complexes are efficient catalysts in the hydrogenation of oximes, with alkoxy-substituted aryl ketimine ligands providing the best catalytic performance. The stable iridium C,N-chelation is crucial for the catalytic activity, and the hydrogenation system demonstrates high functional group compatibility.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Jing Wang, Wenji Wang, Xiongyu Yang, Jingwen Liu, Haizhou Huang, Mingxin Chang
Summary: In this study, a practical homogeneous direct reductive amination (DRA) procedure using iridium catalysis was reported. The reaction conditions were mild and additive-free, allowing for the formation of structurally and functionally diverse amine products, including drugs and compounds from late-stage manipulation. DFT studies revealed that the reaction proceeds via an outer-sphere H-addition pathway with important roles played by pi-pi interactions and H-bonding.
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Gyorgy Hanko, Richard Marton, Antal Udvardy, Mihaly Purgel, Agnes Katho, Ferenc Joo, Gabor Papp
Summary: The water-soluble cis,mer-[IrH2Cl(mtppms)3] was an effective catalyst for the reduction of terminal alkynes by hydrogen transfer, with the highest rate observed at pH 3. The reactions exclusively yielded corresponding alkenes as products, with excess mtppms ligand inhibiting the reaction by forming a less active complex. The joint mechanism for both hydrogenation and transfer hydrogenation pathways was suggested based on experimental results and DFT calculations.
INORGANICA CHIMICA ACTA
(2021)
Article
Energy & Fuels
Wenxuan Xue, Conghui Tang
Summary: This article summarizes the recent progress in the hydrogenation of CO2 or CO2 derivatives to methanol using homogeneous catalysts and molecular hydrogen as the reductant. Discussions on the catalytic systems, efficiencies, and future outlooks are given.
Article
Chemistry, Multidisciplinary
Jonathan Trouve, Paolo Zardi, Shaymaa Al-Shehimy, Thierry Roisnel, Rafael Gramage-Doria
Summary: Utilizing secondary interactions between substrates and catalysts is a promising approach to discover selective transition metal catalysts for atom-economy C-H bond functionalization. The most powerful catalysts are often discovered through trial-and-error screening, as small stereo-electronic modifications within the substrate and catalyst can lead to vastly different reactivities.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Multidisciplinary
Raktim Sen, Alain Goeppert, G. K. Surya Prakash
Summary: The traditional economy based on carbon-intensive fuels and materials has led to a significant increase in anthropogenic CO2 emissions, directly linked to global warming. The methanol economy, with its core concept of chemically recycling CO2 to produce green methanol, offers a prime opportunity for achieving carbon neutrality. Homogeneous catalytic systems have recently emerged as a major research focus for synthesizing methanol from CO2 as a low-temperature alternative to commercial processes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Inorganic & Nuclear
Xiu-Fang Mo, Shun Ge, Ping-Ping Yi, Guo Chen, Jia-Hao Liu, Chao Liu, Xiao-Yi Yi, Piao He
Summary: A series of Cp*Ir complexes with N^N or N^O ancillary ligands were designed and synthesized, and it was found that the pendant base in metal complexes plays a key role in rate-determining heterolytic H2 splitting and enhancing the proton transfer, thereby improving the catalytic activity.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Laurynas Gausas, Bjarke S. Donslund, Steffan K. Kristensen, Troels Skrydstrup
Summary: Polyurethane (PU) is a commonly used thermoset plastic with complex structure, leading to challenges in recycling. The study shows that catalytic hydrogenation of PU materials using a manganese catalyst can effectively deconstruct PU into original monomer components for efficient recovery.
Article
Chemistry, Physical
Anne K. Ravn, Nomaan M. Rezayee
Summary: This study investigates a switchable Cp*-iridium catalyst supported by a 1,10-phenanthroline-2,9-diol for the hydrogenation of amides. The catalyst can selectively induce either C-O or C-N bond scission of the amide depending on the reaction conditions. The addition of base can switch the selectivity to favor C-N bond-cleaved products. These studies provide fundamental insights for the rational design of hydrogenation catalysts.
Article
Chemistry, Multidisciplinary
Thomas Diehl, Patrick Lanzerath, Giancarlo Francio, Walter Leitner
Summary: This study achieved the catalytic conversion of CO2 and hydrogen to methanol using a self-separating multiphasic system. The catalyst phase, composed of the tailor-made complex [Ru(CO)ClH(MACHO-C-12)], demonstrated effective recycling and separate phase formation for product isolation and catalyst separation.
Article
Chemistry, Multidisciplinary
Niklas F. Both, Anke Spannenberg, Haijun Jiao, Kathrin Junge, Matthias Beller
Summary: The use of bis(NHC) manganese(I) complexes 3 as catalysts for the hydrogenation of esters was investigated. Various aromatic and aliphatic esters were successfully hydrogenated at mild temperatures and low catalyst loadings using complexes 3 with KHBEt3 as additive, highlighting the efficiency of the novel catalytic system. Additionally, the versatility of the developed catalytic system was demonstrated by the hydrogenation of other substrate classes like ketones, nitriles, N-heteroarenes, and alkenes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Soumyadeep Chakrabortty, Katharina Konieczny, Felix J. de Zwart, Eduard. O. Bobylev, Eszter Barath, Sergey Tin, Bernd H. Mueller, Joost N. H. Reek, Bas de Bruin, Johannes G. de Vries
Summary: Researchers achieved enantioselective hydrogenation of cyclic enamides using an earth-abundant cobalt-bisphosphine catalyst. The catalytic system, CoCl2/(S,S)-Ph-BPE, reduced trisubstituted carbocyclic enamides to saturated amides with high activity and excellent enantioselectivity (up to 99%). The methodology can be extended to the synthesis of chiral amines by base hydrolysis of the hydrogenation products. Preliminary mechanistic investigations suggested a sigma-bond-metathesis pathway for the hydrogenation of the carbon-carbon double bond, involving a high spin cobalt (II) species.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Inorganic & Nuclear
Naoya Onishi, Yuichiro Himeda
Summary: This paper summarizes the catalysts used in methanol synthesis and dehydrogenation processes, and discusses the potential of these methods for reducing atmospheric CO2 concentration.
COORDINATION CHEMISTRY REVIEWS
(2022)
Article
Chemistry, Multidisciplinary
Wei Zhao, Wenji Wang, Huan Zhou, Qishan Liu, Zhiqing Ma, Haizhou Huang, Mingxin Chang
Summary: A one-pot asymmetric hydrogenation of pyridines with subsequent N-alkylation using a traceless Bronsted acid activation strategy is reported. The reaction exhibits high stereoselectivity and can be used to synthesize indolizidines and quinolizidines. Experimental and theoretical studies reveal that chloride anion and noncovalent interactions play important roles in determining the stereoselectivity of the reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Haibo Wu, Hao Su, Erik J. Schulze, Bram B. C. Peters, Mark D. Nolan, Jianping Yang, Thishana Singh, Marten S. G. Ahlquist, Pher G. Andersson
Summary: The study presents a highly efficient desymmetrization of 1,4-dienes through iridium-catalyzed site- and enantioselective hydrogenation, allowing the installation of two adjacent stereogenic centers. High yields and excellent selectivities were achieved for a range of substrates, and the methodology was demonstrated by synthesizing key intermediates of natural products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Akihiro Tsurusaki, Hiroki Shimatani, Ken Kamikawa
Summary: The gold(I)-catalyzed intramolecular hydroarylation of o-ethynylarylphosphonium salt results in the formation of phosphonium and phosphinium salts. The key to success in this reaction is the use of methylphosphonium salt instead of phosphine chalcogenide. Substrates with different substituents at the alkyne position lead to the formation of different cyclic products, and theoretical calculations show that steric effects influence the activation energy of the reaction.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Rikako Ura, Akihiro Tsurusaki, Ken Kamikawa
Summary: This article reports the complexation of a new bidentate ligand with palladium(II) species. It is found that different compounds can be obtained by reacting with different reagents, and theoretical calculations are used to reveal the properties and reaction processes of these compounds.
DALTON TRANSACTIONS
(2022)
Review
Biochemistry & Molecular Biology
Naoya Onishi, Ryoichi Kanega, Hajime Kawanami, Yuichiro Himeda
Summary: This article provides an overview of recent advances in the research on hydrogen generation by formic acid dehydrogenation, focusing primarily on the development of homogeneous catalysts, which can accelerate the transition to a hydrogen-based society.
Review
Chemistry, Physical
Mingxu Liu, Yuankang Xu, Yu Meng, Lijiao Wang, Hang Wang, Yichao Huang, Naoya Onishi, Lin Wang, Zhuangjun Fan, Yuichiro Himeda
Summary: Given the drastic increase of global carbon dioxide, renewable energy is crucial for maintaining worldwide economic growth. This review focuses on the development of a hydrogen storage system based on formic acid (FA) through CO2 hydrogenation and FA dehydrogenation. Metal catalysts at the nanoscale and single-atom scale are highlighted, as well as the effects of metal size on catalytic activities. The review also emphasizes the structure-activity relationships of various supported catalysts and provides mechanistic insights for rational catalyst design.
ADVANCED ENERGY MATERIALS
(2022)
Article
Multidisciplinary Sciences
Yuichi Manaka, Yuki Nagata, Keisuke Kobayashi, Daisuke Kobayashi, Tetsuya Nanba
Summary: This paper investigates a simple screening method for catalysts that can be used for renewable energy by combining three catalyst evaluation methods. The combination of evaluation methods can intuitively provide the necessary information for catalyst screening.
SCIENTIFIC REPORTS
(2022)
Review
Chemistry, Inorganic & Nuclear
Naoya Onishi, Yuichiro Himeda
Summary: This paper summarizes the catalysts used in methanol synthesis and dehydrogenation processes, and discusses the potential of these methods for reducing atmospheric CO2 concentration.
COORDINATION CHEMISTRY REVIEWS
(2022)
Article
Chemistry, Physical
Keisuke Kobayashi, Yuichi Manaka, Tetsuya Nanba
Summary: The conversion of nitrogen monoxide (NO) to ammonia (NH3) over copper (Cu) catalysts was investigated. It was found that Cu/CeO2 exhibited high NH3 selectivity for the NO-CO-H2O reaction at temperatures above 150 degrees C, while NH3 formation in the NO-H2 reaction was almost negligible at this temperature. The enhancement of the water-gas shift reaction was proposed to be effective in the conversion of NO to NH3.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Inorganic & Nuclear
Wan-Hui Wang, Wei-Yu Shao, Jia-Yue Sang, Xu Li, Xiaoqiang Yu, Yoshinori Yamamoto, Ming Bao
Summary: This article describes an efficient direct N,N-dialkylation of acyl hydrazide using methanol or ethanol as the alkyl reagent under weak base conditions catalyzed by amidato iridium complexes bearing an electron-donating group in the ligand. A wide range of acyl hydrazide derivatives are successfully converted into the corresponding N,N-dialkylated products in excellent yields. The experimental results suggest that ortho electron-donating groups on the phenyl moiety of the picolinamide ligand play a crucial role in the catalytic activity.
Article
Chemistry, Multidisciplinary
Ryoichi Kanega, Erika Ishida, Takaaki Sakai, Naoya Onishi, Akira Yamamoto, Hiroki Yasumura, Hisao Yoshida, Hajime Kawanami, Yuichiro Himeda, Yukari Sato, Akihiro Ohira
Summary: This paper reports a flow battery system using CO2 and formate for storage and generation of electricity, exhibiting good cycle stability and high discharge capacity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Xin Liu, Wen-Zhe Dong, Yining Liu, Wei-Yu Shao, Yang Li, Xiaoqiang Yu, Yuichiro Himeda, Wan-Hui Wang, Ming Bao
Summary: Transition-metal-catalyzed acceptorless dehydrogenative coupling (ADC) is a sustainable strategy for synthesizing N-heteroaromatics. Water-soluble amidato Ru catalysts were designed, synthesized, and used to selectively synthesize 2-substituted benzimidazoles and 2-substituted quinolines via the ADC strategy in water. Catalyst 1d with a strong electron-donating hydroxyl group showed the best catalytic activity.
Article
Chemistry, Multidisciplinary
Yoshihiro Goto, Masashi Kikugawa, Keisuke Kobayashi, Yuichi Manaka, Tetsuya Nanba, Hideyuki Matsumoto, Mitsuru Matsumoto, Masakazu Aoki, Haruo Imagawa
Summary: A facile method was developed to prepare BaTiO2.5H0.5 oxyhydride nanoparticles on a TiH2 surface via the conventional wet impregnation method using TiH2 and Ba hydroxide. The Ru-loaded catalyst Ru/BaTiO2.5H0.5-TiH2 exhibited significantly higher ammonia synthesis activity than the benchmark Ru catalyst Ru-Cs/MgO due to the suppression of hydrogen poisoning. This study demonstrated the importance of appropriate raw material selection for the formation of BaTiO2.5H0.5 oxyhydride nanoparticles using the conventional synthesis method.
Article
Chemistry, Physical
Siming Ding, Yuichi Manaka, Masayuki Nambo, Wang-Jae Chun, Ikuyoshi Tomita, Ken Motokura
Summary: We have developed a mesoporous-silica-supported Pd complex catalyst that promotes the Tsuji-Trost allylation of dicarbonyl compounds with allylic alcohols. By doping the silicate backbone with aluminum, the acidity of the support is increased, leading to enhanced catalytic activity in allylation.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Physical
Naoya Onishi, Yuichiro Himeda
Summary: CO2 conversion is a vital technology for reducing emissions, and methanol production from CO2 using organometallic catalysts shows promise due to its advantages compared to heterogeneous catalysts. This article provides an overview of the current state of both indirect and direct methods for methanol production from CO2, focusing on the design of organometallic catalysts and reaction processes.
Article
Chemistry, Multidisciplinary
Yuanyuan Kong, Siming Ding, Koichiro Endo, Kiyotaka Nakajima, Yuichi Manaka, Wang-Jae Chun, Ikuyoshi Tomita, Ken Motokura
Summary: The Rh-catalyzed 1,4-addition reaction of arylboronic acid is crucial in the synthesis of beta-arylcarbonyl compounds. This study immobilized Rh complexes and organic functional groups on mesoporous silica, resulting in significantly improved catalytic activity and yield in water. The catalyst showed broad applicability to a variety of arylboronic acids and enones.
Article
Chemistry, Physical
Ken Motokura, Nao Ozawa, Risako Sato, Yuichi Manaka, Wang-Jae Chun
Summary: Utilizing elements such as iron as catalysts instead of precious metals is a key step towards environmentally friendly synthesis. The porous FeO(OH) catalyst on Mg-Al hydrotalcite demonstrated high efficiency in synthesizing 2-substituted quinoline derivatives through dehydrogenative oxidation-cyclization reactions. The process proceeded effectively under non-noble-metal catalysis in air without the need for additional homogeneous bases or solvents.