Article
Chemistry, Multidisciplinary
Tianxiao Jiang, Hongchi Liu, Haocheng Zhang, Hanmin Huang
Summary: The article discusses the importance of transition-metal mediated activation of inert chemical bonds in homogeneous catalysis, as well as the advantages of using alkylarenes and benzylamines in benzylation reactions. The research group's contributions in directed C-H activation, nondirected C-H activation, and C-N bond activation are summarized.
CHINESE JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Tianxiao Jiang, Hongchi Liu, Haocheng Zhang, Hanmin Huang
Summary: Activation of inert chemical bonds using transition metals in homogeneous catalysis is a continued focus. The use of alkylarenes and benzylamines as benzyl sources for catalytic benzylation reactions via benzylic C-H and C-N bond activation is highly desirable due to its efficiency and atom-economic nature. This paper summarizes efforts in catalytic benzylation reactions through directed C-H activation, nondirected C-H activation, and C-N bond activation.
CHINESE JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Organic
Xiaoqin Ning, Yongke Chen, Fangdong Hu, Ying Xia
Summary: This study presents the palladium-catalyzed cross-coupling reactions of cyclobutanone-derived N-sulfonylhydrazones with aryl or benzyl halides, demonstrating that the metal carbene process and beta-hydride elimination can occur smoothly in strained ring systems to yield structurally diverse products. The preliminary success in asymmetric carbene coupling reactions in strained ring systems offers a promising route for the synthesis of enantioenriched four-membered-ring molecules.
Article
Chemistry, Organic
Biplab Mondal, Subhadeep Hazra, Ayan Chatterjee, Manveer Patel, Jaideep Saha
Summary: This study developed a catalytic, reductive C-C bond formation method between alkenes and vinyl cyclopropane (VCP) through hydrogen atom transfer (MHAT). Despite the use of VCP as probes in radical-clock experiments, the translation of this method into synthetic methods for accessing elusive C-C bonds remains largely unexplored. This work represents the first exploration in this field, where the high chemoselectivity of MHAT for alkene over VCP was crucial for realizing the strategy. This method has a broad scope, high functional group tolerance, and useful applications.
Article
Chemistry, Multidisciplinary
Barbara Noziere, Fabienne Fache
Summary: This study investigated the reactions of organic peroxy radicals with alkenes at room temperature, showing rate coefficients larger than expected from previous combustion studies. The reactions may not be negligible for some substituted RO2, potentially accounting for a significant portion of their sinks in biogenic-rich regions of the atmosphere.
Article
Chemistry, Physical
Tianbai Huang, Stephan Kupfer, Martin Richter, Stefanie Graefe, Robert Geitner
Summary: A fully conclusive mechanistic picture of the Rh(I)-catalyzed C-H activation and carbonylation is presented using computational methods. The nature of the bisphosphine ligand affects the highest lying transition state, and the rearrangement of chloride ions plays a key role in the subsequent carbonylation. The study suggests that a flexible ligand architecture with aromatic rings can potentially enhance the performance of Rh-based catalysts for C-H activation.
Article
Chemistry, Multidisciplinary
Qinhua Zhang, Bo An, Yu Lei, Zhixiao Gao, Haonan Zhang, Sheng Xue, Xin Jin, Wengang Xu, Zihan Wu, Mingbo Wu, Xin Yang, Wenting Wu
Summary: Developing new reactive pathway to activate inert C(sp3) H bonds for valuable oxygenated products remains a challenge. We prepared a series of triazine conjugated organic polymers to photoactivate C H into aldehyde/ketone via O2!H2O2!*OH!Cl *!Cl2 *. Experiment results showed Cl2 * could successively activate C(sp3) H more effectively than Cl * to generate unstable dichlorinated intermediates, increasing the kinetic rate ratio of dichlorination to monochlorination by a factor of 2,000 and thus breaking traditional dichlorination kinetic constraints. These active intermediates were hydrolyzed into aldehydes or ketones easily, when compared with typical stable dichlorinated complexes, avoiding chlorinated by-product generation. Moreover, an integrated two-phase system in an acid solution strengthened the Cl2 * mediated process and inhibited product overoxidation, where the conversion rate of toluene reached 16.94 mmol/g/h and the selectivity of benzaldehyde was 99.5%. This work presents a facile and efficient approach for selective conversion of inert C(sp3) H bonds using Cl2 *.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Floriane Doche, Julien Escudero, Fabien Petit-Cancelier, Heng-Ying Xiong, Samuel Couve-Bonnaire, Davide Audisio, Thomas Poisson, Tatiana Besset
Summary: This study investigated the unprecedented Pd-catalyzed (ethoxycarbonyl)difluoromethylthiolation reaction and successfully functionalized unsaturated derivatives under mild reaction conditions, providing a new method for synthesis.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Review
Chemistry, Organic
Priyank Purohit
Summary: This article presents the challenge of regiospecific and atom economic C-C bond formation, which has been addressed by directing group and organometal-based C-H activation strategy. Organometals like Ru, Pd, Pt, Ni have been discovered as effective catalysts for C-H activation without the need for pre-activation of the inert C-H bond. This study focuses on cationic ruthenium and its unique reactivity with inert substrates.
CURRENT ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Guilherme L. Tripodi, Magda M. J. Dekker, Jana Roithova, Lawrence Que
Summary: Reactivity of non-heme iron(IV)-oxo complexes is mainly controlled by the ligands, with complexes featuring tetradentate ligands showing the highest reactivity. Fine-tuning of the reactivity of these complexes can be achieved by attaching additional ligands in solution, with the ArIO oxidant playing a previously unknown role. The reactivity of the complexes correlates with the Fe=O and FeO-H stretching vibrations, with the most reactive complex in the series having the weakest Fe=O bond and forming the strongest FeO-H bond.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Inorganic & Nuclear
Seiji Ogo, Takeshi Yatabe, Hidetaka Nakai
Summary: This review discusses whether the ligand design used in catalysts mimicking O2-tolerant [NiFe] hydrogenase can be applied to ligand design in catalysts for C-C bond forming reactions. It explores the possibility of applying the ligand design methodology in reductive C-C coupling and C-H arylation reactions.
COORDINATION CHEMISTRY REVIEWS
(2022)
Article
Chemistry, Physical
Monica Rodriguez, Aleksandr Y. Pereverzev, Jana Roithova
Summary: A novel octahedral non-heme iron-acyl-nitrenoid complex was presented, and its reactivity was studied using a flow chemistry setup with online mass spectrometry detection. It was found that the iron-acyl-nitrenoid complex can activate C-H bonds via hydrogen-atom transfer and form new N-S bonds in the reaction with thiophenol. However, the reaction with hydrocarbons results in the activation of C-H bonds without a subsequent rebound process.
Article
Chemistry, Multidisciplinary
Mitsuhiro Ueda, Kazuya Kamikawa, Takahide Fukuyama, Yi-Ting Wang, Yen-Ku Wu, Ilhyong Ryu
Summary: A novel method has been developed for site-selective alkenylation of a broad variety of substrates, including sterically hindered acyclic and alicyclic substrates. This method allows for the generation of (E)-2-alkylvinylphenylsulfones in high yield by utilizing persulfate and 1,2-bis(phenylsulfonyl)ethene. The compact size of the sulfate radical employed in C-H activation and cleavage allows for the alkenylation of sterically hindered C-H bonds, broadening the scope of substrates that can be efficiently transformed.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Biochemical Research Methods
Dali Fu, Sara Girmay Habtegabir, Haodong Wang, Shijie Feng, Yehua Han
Summary: Multifunctional compounds can form different prototropic isomers known as protomers/deprotomers under different conditions. These isomers affect the interaction modes and conformational landscape between compounds and enzymes, leading to different biological activities. Mass spectrometry and computational chemistry have been proven to be powerful methods for studying prototropic isomers, providing structural information and predicting thermodynamic stability. This review covers various MS methods and theoretical calculations and their contribution to isomer discrimination, structure identification, and conformational transformation of protomers/deprotomers.
ANALYTICAL AND BIOANALYTICAL CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Jonathan Martinez-Laguna, Andres Mollar-Cuni, David Ventura-Espinosa, Santiago Martin, Ana Caballero, Jose A. Mata, Pedro J. Perez
Summary: In this study, a novel strategy was developed to functionalize C-H bonds of cyclohexane and benzene with the assistance of nanoparticulated gold catalyst. The catalyst showed exceptional activity and recyclability.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Wei Li, Hechen Wu, Xunlei Ding, Xiaonan Wu
Summary: The cycloaddition reactions of methane and ethylene mediated by Ir+ have been studied using mass spectrometry and theoretical calculations. The results show that Ir+ can facilitate the cycloaddition reaction to generate a half-sandwich structure IrHCp+ including a pentamethylcyclopentadienyl ligand. The study provides insights into the reaction mechanism and may guide the design of new catalysts with improved selectivity and efficiency.
CHINESE CHEMICAL LETTERS
(2023)
Article
Chemistry, Physical
Zeng Hong, Chao Qian, Shaodong Zhou
Summary: An efficient 3d metal-catalyzed reductive amination method is developed, which employs carbonyl compounds, amines, and molecular hydrogen as substrates to produce secondary or tertiary amines. The combination of EDTA as a skeleton ligand, HBF4 as a promotor, and isopropanol as a hydrogen shuttle enables efficient hydrogenation of imine intermediates. The mechanisms are elucidated through control experiments and DFT calculations, providing insights into the role of each component in the catalytic system.
MOLECULAR CATALYSIS
(2023)
Article
Nanoscience & Nanotechnology
Shuyue Wang, Chao Qian, Shaodong Zhou
Summary: In this work, the potential active V-N center was obtained through theoretical prediction and successfully constructed on N-doped carbon materials. The catalyst exhibited excellent electrocatalytic performance for nitrogen reduction reaction with high faradaic efficiency and NH3 yield rate. Structural characterization and density functional theory calculations confirmed the high performance of the catalyst originated from the tuned d-band upon coordination with nitrogen, in line with the original design intention. Such a rational design-controllable synthesis-theoretical verification strategy may be effective for other chemical processes as well.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Physical
Linghui Yan, Chao Qian, Shaodong Zhou
Summary: The performance of heteronuclear clusters [AlXO3](+) in activating methane was studied using high-level quantum calculations and reported and supplementary gas-phase experiments. The mechanism, reactivity, and selectivity towards methane activation varied with different dopants in [AlXO3](+). The classic HAT and PCET reactions competed depending on the composition of intramolecular interactions. Rational doping was discussed to regulate the activity and selectivity of the catalyst's active center.
Article
Chemistry, Physical
Shihan Li, Xiao-Nan Wu, Shaodong Zhou
Summary: Gas-phase reactions of [OsC3](+) with methane at ambient temperature were studied using quadrupole-ion trap mass spectrometry combined with quantum chemical calculations. Comparison with product clusters revealed significant changes in cluster reactivity. Theoretical calculations showed that electronic features such as molecular polarity index, charge and spin distribution, and HOMO-LUMO gap had an influence on the reactivity of the Os complexes. The polarity of the clusters played a fundamental role in the methane activation. Lowering the local polarity of the catalyst active site may reduce the formation of byproducts in the reaction.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Nanoscience & Nanotechnology
Shuyue Wang, Chao Qian, Shaodong Zhou
Summary: First-principles calculations combined with machine learning were used to design transition-metal single-atom catalysts. Descriptors were selected to describe the nitrogen activation capability of metals and coordinating atoms. Through computational investigation, a series of V/Nb/Ta-N- x single-atom catalysts with promising stability, activity, and selectivity were identified. Moreover, accurate prediction of the hydrogenation barriers for the nitrogen reduction reaction (NRR) was achieved using the gradient boosting regression algorithm.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Physical
Kui Du, Minghao Sun, Jiehai Peng, Shaodong Zhou, Guodong Sheng, Runpu Shen, Liping Deng, Chunqi Hu, Yue Sun, Pengfei Zhang
Summary: In this study, various mixed-valence Pd single-atom catalysts (SACs) were prepared via photodeposition. The electronic structure and dispersion state of the surface Pd species were confirmed, and the important role of graphene oxide in the design of atomically dispersed Pd species was further confirmed. These mixed-valence Pd SACs exhibited excellent catalytic activity for palladium-catalyzed Suzuki and Sonogashira C-C coupling. The mechanism for tailoring the Pd0/Pd2+ atomic ratios was determined using theoretical calculations and EXAFS spectra. These studies open up a wide range of applications for mixed-valence metal-based SACs.
APPLIED SURFACE SCIENCE
(2023)
Article
Chemistry, Physical
Linghui Yan, Bowei Yuan, Chao Qian, Shaodong Zhou
Summary: The performance of heteronuclear cluster [AlFeO3](+) in activating methane has been investigated using high-level quantum chemical calculations and gas-phase experiments. It was found that [AlFeO3](+) exists in two different states, leading to different reactivity and chemoselectivity for methane activation. Furthermore, the introduction of an external electric field can regulate the reactivity and product selectivity. The interesting doping effect of Fe and its associated electronic origins were discussed, which may guide the design of Fe-involved catalysts for methane conversion.
Article
Engineering, Chemical
Xinpei Wang, Chao Qian, Shi-Ya Tang, Shaodong Zhou
Summary: This study couples ammonia synthesis with methane conversion under plasma conditions using Fe-Al composite metal oxides as catalyst, resulting in shortened process for ammonia production and high selectivity in generating C-2 hydrocarbon byproducts. To overcome the activation barrier for methane and nitrogen, dielectric barrier discharge technology is employed to input high-quality energy into the reaction system. Examination of various 3d-metal oxides, SiO2, and Al2O3 leads to the identification of Fe-Al composite metal oxide as the catalyst of choice. The catalyst's structure is characterized using XRD, XPS, TGA, and BET techniques.
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
(2023)
Article
Chemistry, Inorganic & Nuclear
Jin Lv, Mincheng Yu, Jie Qin, Shaodong Zhou
Summary: This study investigates the liquid-phase activation of methane by ruthenium complexes using experiments and quantum-chemical calculations. It is surprising that methane can be efficiently converted to methyl trifluoroacetate under mild conditions, with the bis(NHC) ligand performing better than the other ligands. The study discusses the electronic origins of the exceptional performance of the ruthenium complex, focusing on ligand effects, and identifies the dative C & RARR; Ru interaction and structural distortion of the bis(NHC) plane as responsible factors. This work highlights the promising role of ruthenium in the development of efficient organometallic catalysts for methane conversion.
INORGANICA CHIMICA ACTA
(2023)
Article
Chemistry, Physical
Shi-Ya Tang
Summary: The influence of metal centers on CO2 activation in effective CO2 hydrogenation for producing valuable chemical oxygenates has been investigated. Through experimental and computational methods, it was found that the electron-deficient metal center plays a crucial role in the CO2 insertion process. The reactivity of different metal hydride complexes with CO2 can be estimated by the NBO charge on metals.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Engineering, Chemical
Chao Li, Xiao Zhu, Shiqiang Wang, Yafeng Guo, Yu Du, Yinxia Guan, Shiya Tang
Summary: In this study, a tubular multilayer dielectric barrier discharge (TM-DBD) reactor was developed to decompose butene. The experimental results showed high decomposition efficiency and selectivity under specific conditions. Analysis of the organic byproducts identified different products in different atmospheres. Additionally, three main pathways of butene destruction were proposed.
Article
Chemistry, Physical
Lanxiang Yang, Shuyue Wang, Chao Qian, Shaodong Zhou
Summary: The synthesis of VS4-140 material and its excellent performance in electrocatalytic nitrogen reduction are reported in this study. VS4-140 exhibits a NH3 yield of 46.74 mu g h(-1) mg(cat)(-1) and a faradaic efficiency (FE) of 8.5% at -0.59 V (vs RHE), surpassing VS2. First-principles calculations reveal the distinct behaviors of VS2 and VS4-140 in both reaction mechanism and electronic origins. The preferential alternative pathway for nitrogen reduction is identified in VS4-140. This work highlights the promising potential of vanadium tetrasulfide in nitrogen reduction and provides insights for the design of more efficient catalysts.
ACS APPLIED ENERGY MATERIALS
(2023)
Article
Chemistry, Physical
Shihan Li, Chao Qian, Xiao-Nan Wu, Shaodong Zhou
Summary: Gas-phase reactions of [MC]+ (M = Os and Ru) with methane at ambient temperature have been studied by using quadrupole-ion trap (Q-IT) mass spectrometry combined with quantum chemical calculations. Theoretical calculations reveal the influence of electronic signatures and that it is the energy gap of the associated frontier molecular orbitals that dominates the ability of the cluster in the initial H3C-H bond breaking. Additionally, factors like the dipole moment, spin density, and charge distributions influence the orbital energy gap to different extents, suggesting that altering the local structure of the active center could regulate the activity.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Zihan Lv, Zeng Hong, Chao Qian, Shaodong Zhou
Summary: Pt-Pd alloy nano-catalysts supported on TiO2 were developed for efficient light-induced photocatalytic N-alkylation of amines with alcohols. Various techniques were utilized to characterize the catalysts and the photocatalytic mechanism was discussed. Pt served as a hydrogen shuttle, extracting hydrogen from alcohols to Pd for subsequent hydrogenation. By adjusting the Pd/Pt ratio, the reaction rates of methanol dehydrogenation and imine hydrogenation could be tuned simultaneously, leading to an efficient N-alkylation reaction. The Pd1Pt1/TiO2 catalyst exhibited excellent catalytic performance surpassing previous reports in terms of both efficiency and capacity.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
