Article
Chemistry, Physical
Ronen Kruchinin, Oswaldo Dieguez
Summary: In this article, density-functional theory calculations are used to study the energetics of CO2 reduction to methane via the Sabatier reaction on sulfur-based transition-metal dichalcogenides (TMDs) with non-, Ni- and Cu-doping. It is found that sulfur-based TMDs with Ni/Cu doping exhibit better indicators for catalytic performance of the CO2 reduction reaction compared to non-doped and doped TMDs without active sites. Furthermore, the role of the chalcogen and dopant atoms in influencing bonding strength and type is found to have a much bigger influence on the reaction than the transition metal.
Article
Chemistry, Multidisciplinary
Kaixue Xie, Martin Oestreich
Summary: Readily available cyclohexa-2,5-dien-1-ylcarbonyl chloride derivatives were used as stable HCl surrogates for transfer hydrochlorination of alkenes and alkynes. B(C6F5)(3) facilitated the stepwise fragmentation of acyl chlorides, allowing the addition of HCl across C-C double and triple bonds with Markovnikov selectivity at room temperature.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Inorganic & Nuclear
Feda'a M. Al-Qaisi, Abdussalam K. Qaroush, Ibrahim K. Okashah, Ala'a F. Eftaiha, Petra Vasko, Fatima Alsoubani, Timo Repo
Summary: By following green chemistry principles, a zinc curcumin complex was synthesized and used as a sustainable catalyst for the synthesis of cyclic carbonate from CO2 and epoxides. The complex exhibited outstanding catalytic activity and showed potential for the synthesis of renewable carbonates.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Kellsie Jurkowski, Eike B. Bauer
Summary: Ferrocenium cations are used as catalysts in organic transformations, and their decomposition rate constants depend on the nature of the counterion, with oxidative process being the main decomposition pathway. The cosolvent and changes in counterions can influence the catalytic activity.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Multidisciplinary
Raphael Robidas, Claude Y. Legault
Summary: A mechanism is proposed to explain the formation of benzobicyclo[3.2.0]heptane derivatives from 1,7-enyne derivatives bearing a terminal cyclopropane, which has been previously reported.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Review
Chemistry, Multidisciplinary
Niklas W. Kinzel, Christophe Werle, Walter Leitner
Summary: The electrocatalytic transformation of carbon dioxide has long been a topic of interest, with recent focus on it as an alternative strategy for CO2 reduction. Studies have increasingly looked at direct electron transfer and molecular transition metal complexes as catalysts. This can lead to the production of C-1 compounds as well as more complex transformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Multidisciplinary
Lu-Hua Zhang, Simon Mathew, Joeri Hessels, Joost N. H. Reek, Fengshou Yu
Summary: The pursuit of renewable production of storable fuels through electrocatalysis, particularly with water oxidation catalysis, remains a key focus in the scientific community. The coupling of these redox transformations to renewable energy sources presents a carbon neutral solution for long-term energy storage, yet challenges such as scalability still need to be addressed.
Review
Chemistry, Multidisciplinary
Abhishek Kumar, Shrivats Semwal, Joyanta Choudhury
Summary: Transition-metal-catalyzed hydride-transfer reactions play a crucial role in building a sustainable energy economy, with a focus on H-2 evolution and CO2 reduction/hydrogenation catalysis. Therefore, understanding the hydricity of transition-metal hydrides and its influencing factors is essential for designing efficient catalysts.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Xavier Deraet, Jan Turek, Mercedes Alonso, Frederik Tielens, Bert M. M. Weckhuysen, Monica Calatayud, Frank De Proft
Summary: This paper investigates the adsorption behavior of single late transition metals on a defect-free anatase surface using periodic density functional theory calculations. The results reveal that the interaction strength between the transition metals and the support can be attributed to electron transfer, s-d orbital hybridization effects, or a synergistic effect between both factors. Palladium shows deviating adsorption behavior, which is likely associated with the lower dissociation enthalpy of the Pd-O bond. The reactivity of these systems is evaluated using the Fermi weighted density of states approach, and a model is proposed to predict the adsorption strength of CO on anatase-supported d-metal atoms.
Review
Chemistry, Organic
Lucas Pages, Racha Abed Ali Abdine, Florian Monnier, Marc Taillefer
Summary: This article introduces the widespread exploration of intermolecular transition-metal catalyzed hydroarylation of allenes since the early 1980s. This reaction allows the selective access to high-value allylic or vinylic motifs through the formation of C-C bonds. The article also mentions the use of arenes, organoboronic derivatives, and aryl halides as aryl sources, as well as the use of gold, palladium, and other transition metals as catalysts.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Xavier Deraet, Jan Turek, Mercedes Alonso, Frederik Tielens, Stefaan Cottenier, Paul W. Ayers, Bert M. Weckhuysen, Frank De Proft
Summary: The study focused on single-atom catalysis using density functional theory, revealing the sensitivity of silver and gold atoms to van der Waals dispersion forces, and the role of oxophilicity in the interaction strength of late transition metals on the SiO2 support. Adsorption energies varied between -1.40 to -1.92 eV for row 4 elements, and between -2.20 to -2.92 eV for heavier metals, except for Pd. The Fermi weighted density of states approach was identified as the most suitable for describing reactivity trends and showed good agreement with experimental data.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Shuo Wang, Shao-Yang Feng, Cong-Cong Zhao, Ting-Ting Zhao, Yu Tian, Li-Kai Yan
Summary: Anchoring transition metal atoms on graphdiyne as catalysts for CO2 reduction significantly improves the catalytic activity. Cu-1-GDY shows excellent electrocatalytic activity for CO2 reduction to HCOOH, with a limiting potential of -0.16 V. Mn-1-GDY and Co-1-GDY exhibit superior catalytic selectivity for CO2 reduction to CH4, with limiting potentials of -0.62 and -0.34 V, respectively. This study provides a solid theoretical basis for the conversion of CO2 into valuable hydrocarbons.
Review
Chemistry, Multidisciplinary
Juba Ghouilem, Morgane de Robichon, Franck Le Bideau, Angelique Ferry, Samir Messaoudi
Summary: Transition-metal-catalyzed C-H functionalization and photoredox nickel dual catalysis are innovative approaches for the synthesis of C-branched glycosides, providing efficient and mild methods for accessing a variety of complex C-branched glycosides of great interest.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Arputham Shophia Lawrence, Balasubramanian Sivakumar, Amarajothi Dhakshinamoorthy
Summary: Metal organic frameworks (MOFs) are important heterogeneous solid catalysts with a wide range of active sites, particularly Lewis acids, which play a key role in organic reactions. Experimental evidence supports the presence of these active sites, and density functional theory (DFT) calculations are used to complement and clarify their role in catalytic reactions. Theoretical evidence is crucial in providing a deeper understanding of MOFs' role in promoting reactions and supporting proposed reaction mechanisms.
MOLECULAR CATALYSIS
(2022)
Review
Chemistry, Multidisciplinary
Lionel Massi, Jean-Francois Gal, Elisabet Dunach
Summary: Metal triflates have demonstrated their applicability as catalysts in various organic reactions, primarily in C-O and C-C bond formation. Understanding the interaction between Lewis acids and organic functional groups as ligands helps in selecting suitable metal cations for specific reactions. Electrospray ionization mass spectrometry provides a means for characterizing and quantifying donor/acceptor interactions involved in catalytic processes. By using ligand displacement experiments, quantitative affinity scales of ligands towards metal centers can be established.
Review
Chemistry, Multidisciplinary
Yoshiaki Nakao
Summary: Nitriles are versatile building blocks in organic synthesis, with common reactions including transformations of cyano groups. While the C-CN bond of nitriles is thermodynamically robust and rarely used as a reaction site, metal-catalyzed reactions have shown the potential for activation. These reactions are categorized into those using CN as a leaving group and those utilizing nitriles as a source of CN groups, offering new possibilities for organic synthesis.
Article
Chemistry, Multidisciplinary
Kazuhiko Semba, Naoki Ohta, Fritz Paulus, Masaki Ohata, Yoshiaki Nakao
Summary: This new method allows for allylarylation of electron-deficient alkenes using aryl boronates and allylic carbonates as starting materials, leading to a variety of carbon skeletons. Mechanistic studies reveal that the reaction is facilitated by a cooperative catalysis involving Pd-0/Pd-II redox and Pd-II/Pd-II non-redox catalytic cycles.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Jun Chen, Yu-Jie Liang, Peng-Zi Wang, Guo-Qing Li, Bin Zhang, Hao Qian, Xiao-Die Huan, Wei Guan, Wen-Jing Xiao, Jia-Rong Chen
Summary: This study presents a photoinduced copper-catalyzed cross-coupling reaction for the generation of allylic esters. The reaction proceeds at room temperature with high regio- and enantioselectivity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Applied
Qiao-Zhi Li, Naofumi Hara, Kazuhiko Semba, Yoshiaki Nakao, Shigeyoshi Sakaki
Summary: Rh(PAlP) is a new type of catalyst for reactions via sigma-bond activation, showing unique Rh-Al direct bond, flexible substrate coordination, and new catalytic functions for C-H and C-F sigma-bond activations. The unusual Rh delta--Al delta+ polarization and coordination flexibility play important roles in these catalytic reactions.
TOPICS IN CATALYSIS
(2022)
Article
Chemistry, Physical
Run-Han Li, Yu-Long Zhao, Qing-Kun Shang, Yun Geng, Xin-Long Wang, Zhong-Min Su, Guang-Fu Li, Wei Guan
Summary: Photocatalytic coupling reactions have rapidly developed in the field of organic synthesis. A novel metallaphotoredox catalysis utilizing a NaI-PPh3 photoredox catalyst and Cu(I) catalyst was designed and evaluated, achieving high yields of C(sp(3))-O/N cross-couplings of alkyl N-hydroxyphthalimide esters with phenols/secondary amines under mild conditions with only blue light irradiation. This strategy provides a facile and economic route for C(sp(3))-X cross-coupling reactions while also offering a clear mechanistic understanding.
Article
Chemistry, Multidisciplinary
Ru Zhong Zhang, Ru Xue Zhang, Shuang Wang, Cong Xu, Wei Guan, Mang Wang
Summary: In this study, an alternative and scalable cyclization strategy based on NCF3-containing synthons was used to construct N-CF3 azoles. This approach allows for the divergent synthesis of N-trifluoromethylated tetrazoles, imidazoles, and 1,2,3-triazoles using various dipoles. The introduction of CF3 onto the nitrogen of heterocycles provides a direct route to such motifs, overcoming the limitations of traditional methods.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Kazuhiko Semba, Fumiya Shimoura, Yoshiaki Nakao
Summary: A cobalt complex ligated with a PAlP pincer ligand was synthesized and the Lewis acidity of the aluminum atom on the cobalt complex was confirmed by coordination with 4-dimethylaminopyridine (DMAP). Reactions of the cobalt complex with H2O, EtOH, i-PrOH, and t-BuOH efficiently yielded the corresponding cobalt hydride complexes.
Article
Chemistry, Organic
Yuki Naganawa, Yumiko Nakajima, Shigeyoshi Sakaki, Hajime Kameo
Summary: The study elucidated two possible pathways for Si-Cl bond activation in Pd-catalyzed coupling reaction, providing insights for rational catalyst design.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Naofumi Hara, Kazuhiko Semba, Yoshiaki Nakao
Summary: Transition metal complexes with X-type aluminyl ligands exhibit strong reactivity and enable various challenging catalytic transformations such as transfer dehydrogenation, highly efficient CO2 reduction, and site-selective C-H bond functionalization.
Article
Chemistry, Organic
Hajime Kameo
Summary: Polyfunctional ligands containing Lewis acid moieties have shown great potential in transition metal catalysis. Z-type ligands can function as electrophilic catalysts by interacting with the metal center, and they also promote cross-coupling reactions. This article presents two examples of metal-ligand cooperation: Pd-borane cooperation and cross-coupling reactions of fluoro-silanes and -germanes. These examples demonstrate the versatility of Z-type ligands in bond activation and cross-coupling reactions.
JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN
(2022)
Article
Chemistry, Organic
Ikuya Fujii, Kazuhiko Semba, Yoshiaki Nakao
Summary: Rhodium-aluminum bimetallic complexes catalyze the Kumada-Tamao-Corriu (KTC) cross-coupling reaction using arylmagnesium compounds generated from corresponding aryl fluorides or chlorides. This method allows the challenging KTC coupling reaction to be carried out using aryl fluorides as nucleophiles, resulting in various biaryls.
Article
Chemistry, Multidisciplinary
Hajime Kameo, Yudai Tanaka, Yoshihiro Shimoyama, Daisuke Izumi, Hiroyuki Matsuzaka, Yumiko Nakajima, Pierre Lavedan, Arnaud Le Gac, Didier Bourissou
Summary: A T-shaped Pt-0 complex with a diphosphine-borane (DPB) ligand was prepared. The Pt -> B interaction enhances the electrophilicity of the metal and triggers the addition of Lewis bases to give the corresponding tetracoordinate complexes. For the first time, anionic Pt-0 complexes are isolated and structurally authenticated.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Inorganic & Nuclear
Hajime Kameo, Yuki Baba, Hiroyuki Matsuzaka
Summary: The chemistry of Z-type ligands has attracted attention due to their distinctive chemical bonds, properties, and reactivities. A study found that Lewis acidic fluorostannane coordination enhances nucleophilicity, providing new opportunities for Pd-catalyzed cross-coupling reactions. Through phosphine chelation, fluorostannane acts as a Lewis acid and weakens the strong and polar Sn-F bond via a-donation from the Pd center, allowing easy abstraction of the F atom. This enables the catalytic arylation of fluorostannane for the first time.
Article
Chemistry, Inorganic & Nuclear
Yujie Liang, Yujiao Dong, Guangyan Sun, Zhongmin Su, Wei Guan
Summary: This study systematically investigates the mechanism of visible-light-induced inexpensive photocatalyst and transition metal dual catalytic cross-coupling reactions. It reveals key issues such as enantioselectivity and rate-determining steps, providing important references for future catalytic reaction studies.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Multidisciplinary
Yu Gao, Wei Guan, Li-Kai Yan, Ran Jia, Zhong-Min Su
Summary: The internal electric field generated in DSSCs has a significant impact on conversion efficiency, with theoretical calculations showing that higher electric field strength can improve the performance of DSSCs. This study highlights the potential relationship between electric fields and DSSC efficiency.
MATERIALS CHEMISTRY FRONTIERS
(2021)
