Article
Chemistry, Physical
Tamalika Ash, Soumadip Banerjee, Abhijit K. Das
Summary: The catalytic hydrogenation of CO with NH3BH3 using phosphorus compounds has been studied computationally. The initiation step involves the transfer of protic and hydridic hydrogens from NH3BH3 to form an active phosphorus compound. The newly formed catalyst then converts CO to HCHO and MeOH. The efficiency of the phosphorus compounds is compared based on the calculated activation barriers of the rate-determining step.
CHEMICAL PHYSICS LETTERS
(2023)
Article
Chemistry, Physical
Deshuai Yang, Panqing Bao, Zhen Yang, Zhaoxu Chen, Shigeyoshi Sakaki, Satoshi Maeda, Guixiang Zeng
Summary: A theoretical study shows that a metal-free catalyst composed of a phosphorus compound with a boryl-pendant is effective for hydrogen generation from ammonia borane through phosphorus-boryl (P-B) cooperation. The P-B cooperation function plays a crucial role in the catalytic activity, as demonstrated by the inactivity of a pincer-type phosphorus compound without a boryl-pendant.
Article
Chemistry, Multidisciplinary
Qin Zhu, Shuoqi Zhang, Jing Ma, Jun Zhu, Shuhua Li, Guixiang Zeng
Summary: The transfer hydrogenation of azobenzene with ammonia borane mediated by pincer bismuth complex 1 was studied using density functional theory calculations. The study revealed an unusual metal-ligand cooperation mechanism involving the saturation/regeneration of the C=N functional group on the pincer ligand. The reaction proceeds through the hydrogenation of the C=N bond, followed by the conversion of 3(CN) to a Bi-H intermediate, and eventually results in the production of N,N'-diphenylhydrazine and regeneration of the catalyst. The substitution of the phenyl group with a tert-butyl group on the pincer ligand improves the catalyst's performance.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
David Decker, Zhihong Wei, Jabor Rabeah, Hans-Joachim Drexler, Angelika Brueckner, Haijun Jiao, Torsten Beweries
Summary: In this study, a Co(ii) PNNH pincer catalyst system was applied for the highly E-selective transfer semihydrogenation of internal diaryl alkynes. The catalyst system showed high activity, short reaction times, and operated under mild conditions.
INORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Inorganic & Nuclear
Jiarui Chang, Jia-Xue Mao, Man Ding, Jie Zhang, Xuenian Chen
Summary: The catalytic reactivities of group 10 metal hydride complexes supported by a PNCNP pincer ligand towards CO2 reduction with NH3 center dot BH3 and NaBH4 have been investigated. The reactions proceed through the insertion of the C=O bond in CO2 into the metal-hydrogen bond in the complexes, forming formato species and regenerating the metal complexes. This work represents a rare example of catalytic transfer hydrogenation of CO2 to formic acid under mild conditions and the first example of 4 equiv of CO2 uptake by NaBH4.
INORGANIC CHEMISTRY
(2023)
Review
Chemistry, Physical
Wenfeng Zhao, Hu Li, Heng Zhang, Song Yang, Anders Riisager
Summary: Ammonia borane (AB) is a promising material for hydrogen storage and has attracted much attention in reductive organic transformations. This review summarizes the recent progress of AB-mediated transfer hydrogenation reactions of various substrates and discusses the synthesis protocols, reaction parameters, product distribution, and reactivity. The mechanism involving the action mode of AB and structure-activity relationships are also discussed, and the challenges and opportunities for AB-enabled transfer hydrogenation reactions are highlighted.
GREEN ENERGY & ENVIRONMENT
(2023)
Article
Chemistry, Inorganic & Nuclear
Leah K. Oliemuller, Curtis E. Moore, Christine M. Thomas
Summary: A Mn(CO)(2) complex with a central three-coordinate N-heterocyclic phosphorus fragment is synthesized and its reactivity towards H-2, NH3BH3, H+, and H- is investigated. Computational methods and reactivity studies are used to assess the electrophilic nature of the N-heterocyclic phosphenium moiety and the nucleophilic manganese center. The bonding interactions of a synthesized pincer-ligated manganesedicarbonyl complex featuring an N-heterocyclic phosphenium central moiety are explored.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Ying Zhou, Yaqi Zhao, Xiaofan Shi, Yanhui Tang, Zuoyin Yang, Min Pu, Ming Lei
Summary: In this study, a density functional theory (DFT) was used to thoroughly investigate the cascade reaction mechanism for the hydrogenation of carbon dioxide to methanol catalyzed by ruthenium pincer complex [RuH2(Me2PCH2SiMe2)(2)NH(CO)]. The calculated results show that the main H-2 activation strategy in this reaction is formate-assisted H-2 activation. The reaction has a low energy span and can occur under mild conditions. Additionally, the catalyst can efficiently perform transfer hydrogenation using isopropanol as the hydrogen source, and different ruthenium pincer complexes show similar catalytic activities for CO2 hydrogenation to methanol.
DALTON TRANSACTIONS
(2022)
Article
Nanoscience & Nanotechnology
Sila Alemdar, Aleyna Basak, Onder Metin
Summary: In this study, binary red phosphorus/graphitic carbon nitride heterojunctions decorated with Pt nanoparticles were fabricated, showing improved photophysical properties compared to the pristine components. The incorporation of Pt NPs further improved the optical properties and enabled a high hydrogen gas generation rate under visible light irradiation. The interaction between Pt NPs and red phosphorus in the ternary heterojunction was found to be more favorable than that with graphitic carbon nitride. The band alignment and charge carrier flow of the ternary heterojunction catalyst were also studied. The mechanism of the photo-assisted hydrogen production from ammonia borane was proposed to involve both traditional B-N bond dissociation and the oxidizing action of OH radicals formed by the heterojunction photocatalyst.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Energy & Fuels
Wenxiu Luo, Guo Li, Wei Cheng, Yi Wang
Summary: Carbon materials derived from biomass wastes are attractive due to their cost efficiency and abundant natural resources. However, finding suitable synthetic strategies and effective approaches to regulate their properties remains a challenge. In this study, silicon dioxide modified carbonaceous materials from pomelo peel were used as an excellent support for small-size and well-dispersed Rh nanoparticles. The resulting Rh/IPP-SiO2 catalyst exhibited superior catalytic efficiency for ammonia borane dehydrogenation reactions.
Article
Chemistry, Physical
Yong Cheng, Dan Wang, Xiuxiu Wang, Ying-Hua Zhou
Summary: In this study, a high-efficiency tandem catalyst CuO-Ru-0.3@Co3O4 was synthesized for the hydrolytic dehydrogenation of ammonia borane (AB) and the hydrogenation of nitrobenzenes (NBs). The catalyst showed high activity and good cyclic stability.
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
(2022)
Article
Chemistry, Inorganic & Nuclear
Ignacio Chamorro-Mena, Noemi Linares, Javier Garcia-Martinez
Summary: This study describes the optimization of Cu2O/CuO heterostructures for enhanced (photo)catalytic performance. The evaluation of catalysts with different Cu2O/CuO molar ratios revealed that a ratio of 0.15 resulted in significantly higher rate constants under blue-LED light. Furthermore, this photocatalyst exhibited good stability and excellent chemoselectivity in the presence of other functionalities.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Ignacio Chamorro-Mena, Noemi Linares, Javier Garcia-Martinez
Summary: This study explores the optimization of Cu2O/CuO heterostructures for enhancing their (photo)catalytic performance. By evaluating catalysts with different Cu2O/CuO molar ratios, the researchers found that a ratio of 0.15 resulted in significantly higher reaction rate constants under blue LED light compared to lower (0.01) or higher (0.42) ratios. The photocatalyst also demonstrated good stability (>70% after 5 cycles) and excellent chemoselectivity in the selective reduction of the nitro group in the presence of other functionalities, such as -COOH, -CONH2, and -OH.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Physical
Nana Ma, Qingli Xu, Guisheng Zhang
Summary: This paper presents computational progress in the reduction of carbonyl compounds using boron reducing agents and discusses the role of boron reducing agents on reaction efficiency. The establishment of a catalytic mechanism is crucial for improving the combination of reducing agents and catalysts, which varies depending on the combinations of electrophilic boron reducing agents and catalysts. Future opportunities in this research field are also outlined.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
Review
Chemistry, Inorganic & Nuclear
Hugo Valdes, Juan M. German-Acacio, Gerard van Koten, David Morales-Morales
Summary: This study explores the synthesis and applications of bimetallic complexes by merging a metallocene and a (cyclopentadienyl/aryl) pincer metal complex, discussing their importance in tuning electronic properties, catalytic reactions, and chiral catalysis. Various approaches to merge metallocene and pincer-metal motifs are explored, showcasing the potential for creating diastereomerically pure derivatives through post-functionalization strategies. The authors aim to inspire further research in this field by highlighting the synthetic, physico-chemical properties, and remarkable catalytic activities of metallocene-based pincer-metal complexes.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Masato Kobayashi, Yuta Oba, Tomoko Akama, Tetsuya Taketsugu
Summary: This paper proposes a practical electronic calculation method for lanthanide complexes, which introduces the frozen core potential approximation and relaxation of rotational degrees of freedom to improve the accuracy and convergence of the calculations.
JOURNAL OF MATHEMATICAL CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Yu Harabuchi, Hiroki Hayashi, Hideaki Takano, Tsuyoshi Mita, Satoshi Maeda
Summary: Systematic reaction path exploration revealed the entire mechanism of Knowles's light-promoted catalytic intramolecular hydroamination. This study found that bond formation/cleavage competes with single electron transfer and that reduction and proton shuttle processes proceed concertedly.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Physical
Satoshi Maeda, Yu Harabuchi, Hiroki Hayashi, Tsuyoshi Mita
Summary: Predicting the entire process of a chemical reaction and directly discovering chemical reactions and their product yields through kinetic simulations is made possible by narrowing the search space based on the kinetic analysis of the reaction path network. The authors propose a practical method by combining artificial force induced reaction and rate constant matrix contraction methods, offering forward and backward algorithms for this purpose. The effectiveness of these methods is demonstrated through numerical verification and application to actual reaction discovery, highlighting the challenges and prospects of ab initio reaction discovery.
ANNUAL REVIEW OF PHYSICAL CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Geoffrey Roberts, Jonathan Haslam, Satoshi Maeda
Summary: In this study, a workflow employing the AFIR method was used to investigate the self-assembly process of the SIFSIX-3-Zn MOF. Multiple competing pathways involving interconvertible intermediates were identified, providing a plausible explanation for the stochastic multistage processes believed to be key in MOF formation. This work represents the first application of an automated reaction mechanism discovery method to a MOF system.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Atsuyuki Nakao, Yu Harabuchi, Satoshi Maeda, Koji Tsuda
Summary: This research proposes a method based on graph neural networks to optimize the choice of transformation patterns for efficient energy landscape exploration. Artificial force has proven to be useful in overcoming energy barriers and searching a large portion of the energy landscape.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Multidisciplinary
Hideaki Takano, Hitomi Katsuyama, Hiroki Hayashi, Miyu Harukawa, Makoto Tsurui, Sunao Shoji, Yasuchika Hasegawa, Satoshi Maeda, Tsuyoshi Mita
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Hideaki Takano, Hitomi Katsuyama, Hiroki Hayashi, Miyu Harukawa, Makoto Tsurui, Sunao Shoji, Yasuchika Hasegawa, Satoshi Maeda, Tsuyoshi Mita
Summary: In this study, a novel synthetic method for (un)symmetric diphosphines based on the BCP motif is reported. The highly reactive internal C-C bond of [1.1.1]propellane is manipulated to construct disubstituted straight-shaped bicyclo[1.1.1]pentane (BCP) compounds, which are considered isosteres of 1,4-disubstituted benzenes. The obtained BCP-diphosphine derivatives are used to generate a straight-shaped Au complex and an Eu-based coordination polymer.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Eiki Tomita, Masahiro Kojima, Yuki Nagashima, Ken Tanaka, Haruki Sugiyama, Yasutomo Segawa, Atsushi Furukawa, Katsumi Maenaka, Satoshi Maeda, Tatsuhiko Yoshino, Shigeki Matsunaga
Summary: The synthesis, characterization, and catalytic performance of an iridium(III) catalyst with an electron-deficient cyclopentadienyl ligand were reported. The catalyst was synthesized by complexation of a precursor of the electron-deficient ligand with an iridium compound, followed by oxidation, desilylation and removal of another ligand. The electron-deficient catalyst enabled C-H amidation reactions assisted by a weakly coordinating directing group.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Yong Zheng, Julong Jiang, Mingoo Jin, Daiyo Miura, Fei Xue Lu, Koji Kubota, Tasuku Nakajima, Satoshi Maeda, Hajime Ito, Jian Ping Gong
Summary: In this study, a novel strategy for real-time visualization of mechanochemical damages in hydrogels was developed using prefluorescent probes via oxygen-relayed free-radical trapping. This method allows for the detection of mechanochemical damages in hydrogels made from brittle networks of varied chemical structures, without introducing any chemical structural changes in the materials.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Biochemistry & Molecular Biology
Ruben Staub, Philippe Gantzer, Yu Harabuchi, Satoshi Maeda, Alexandre Varnek
Summary: In this article, the feasibility of using Neural Network Potentials (NNP) to accelerate the Artificial Force Induced Reaction (AFIR) method is investigated. A novel theoretical study of ethylene hydrogenation using the AFIR method is reported, and the resulting reaction path network is analyzed. The limitations of general purpose NNP models in such studies are identified, and a solution involving fast semiempirical predictions is proposed to overcome these challenges.
Article
Chemistry, Physical
Taisuke Hasegawa, Satoshi Hagiwara, Minoru Otani, Satoshi Maeda
Summary: This article presents a combined simulation method that combines single-component artificial force induced reaction (SC-AFIR) and effective screening medium combined with the reference interaction site model (ESM-RISM), enabling the exploration of reliable reaction pathways at the solid-liquid interface. It was applied to study the dissociation pathway of an H2O molecule at the Cu(111)/water interface.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Keisuke Tashiro, Masato Kobayashi, Kiyotaka Nakajima, Tetsuya Taketsugu
Summary: A comprehensive reaction-path search using quantum chemical calculations was conducted to understand the mechanism of humin formation in the oxidation of HMF to FDCA. The study identified multiple reaction paths with low barriers for the reaction of HMF with OH-. It was also confirmed computationally that acetal protection of HMF could suppress humin formation.
Article
Chemistry, Multidisciplinary
Kewei Sun, Kazuma Sugawara, Andrey Lyalin, Yusuke Ishigaki, Kohei Uosaki, Oscar Custance, Tetsuya Taketsugu, Takanori Suzuki, Shigeki Kawai
Summary: In this study, complex organometallic oligomers were systematically synthesized on Cu(111) through sequential ring opening and bonding of phenanthroline derivatives by multiple Cu atoms. Characterization using scanning tunneling microscopy and density functional theory calculations revealed the role of Cu adatoms in the chiral oligomers. Furthermore, the strength of the bonds against sliding friction was found to be sufficient.
Article
Chemistry, Multidisciplinary
Satoi Wada, Takuro Tsutsumi, Kenichiro Saita, Tetsuya Taketsugu
Summary: Recently, surface-hopping ab initio molecular dynamics (SH-AIMD) simulations have been used to study the mechanisms and dynamics of excited-state chemical reactions. In this study, the authors investigate the effects of spin-orbit coupling (SOC) on the results of dynamics simulations using spin-pure and spin-mixed states for the hydride MH2 (M = Si, Ge, Sn, Pb). The results show that spin-mixed state potential energy surfaces are essential for simulating intersystem crossing in systems containing Sn and Pb elements.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2023)
Article
Multidisciplinary Sciences
Xihong Wang, Chi Feng, Julong Jiang, Satoshi Maeda, Koji Kubota, Hajime Ito
Summary: This paper reports the synthesis of silicon-stereogenic silylboranes and the generation of silicon-stereogenic silyl nucleophiles with high enantiopurity and configurational stability. The method is applicable to the synthesis of various silicon-substituted boranes and allows for C-Si bond-forming reactions.
NATURE COMMUNICATIONS
(2023)
