Article
Chemistry, Multidisciplinary
Katsuhiko Takeuchi, Ming-Yu Chen, Hao-Yu Yuan, Hiroki Koizumi, Kazuhiro Matsumoto, Norihisa Fukaya, Yoong-Kee Choe, Shinji Shigeyasu, Seiji Matsumoto, Satoshi Hamura, Jun-Chul Choi
Summary: The study successfully isolated and characterized a zinc carbamate complex and proposed an improved catalytic system that can efficiently synthesize various carbamates, including industrially important polyurethane raw materials, using CO2 under atmospheric pressure.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Inorganic & Nuclear
Akira Okumura, Priyabrata Ghana, Fabian Fink, Regina Schmidt, Alexander Hoffmann, Thomas P. Spaniol, Sonja Herres-Pawlis, Jun Okuda
Summary: This study describes titanium(III) and titanium(IV) formate complexes supported by a stericay encumbering tris(phenolato) amine ligand. The authors synthesized various titanium complexes with different coordination numbers and oxidation states through different chemical reactions, and fully characterized them using various analytical methods.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Christian Marvelous, Lucas de Azevedo Santos, Maxime A. Siegler, Celia Fonseca Guerra, Elisabeth Bouwman
Summary: This study describes the reactivity of a selenium-based ligand with cobalt(II) salts and the synthesis of corresponding cobalt(II)-diselenide and cobalt(III)-selenolate complexes. Computational studies suggest that the redox conversion of the selenium compounds is more challenging than that of their sulfur analogs.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Manussada Ratanasak, Takumi Murata, Taishin Adachi, Jun-ya Hasegawa, Tadashi Ema
Summary: BPh3 catalyzes the N-methylation of secondary amines and the C-methylenation of N,N-dimethylanilines or 1-methylindoles in the presence of CO2 and PhSiH3. The mechanism involves the activation of PhSiH3 by BPh3 to generate key CO2-derived species for the N-methylation reaction. DFT calculations also suggest other mechanisms involving water for the activation of PhSiH3.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Physical
Vishnu Nair Gopalakrishnan, Toan-Anh Quach, Jorge Becerra, Sakar Mohan, Jason M. E. Ahad, Francois Beland, Trong-On Do
Summary: In recent decades, there has been growing interest in using visible light-driven photo catalysts to photoreduce carbon dioxide (CO2) into fuels. However, achieving efficient conversion of CO2 with high selectivity has remained a challenge. In this study, researchers developed a hybrid plasmonic covalent organic framework (COF) by combining a hollow porphyrin-based COF with a cobalt (Co) single atom decorated with plasmonic Au nanoparticles (COF-366-Co(H)/Au) to greatly enhance the photoreduction of CO2. This hybrid system showed excellent activity, producing CO with a selectivity of approximately 98% at a rate of up to 1200 mu mol g-1 h-1. The COF-366-Co(H)/Au also exhibited a notable AQY of 0.5% at 420 nm. This research demonstrates the potential of using hollow COFs in combination with single atoms and plasmonic nanoparticles for solar-to-fuel conversion.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Inorganic & Nuclear
Simon Suhr, Nicolai Schroter, Merlin Kleoff, Nicolas Neuman, David Hunger, Robert Walter, Clemens Lucke, Felix Stein, Serhiy Demeshko, Hang Liu, Hans -Ulrich Reissig, Joris van Slageren, Biprajit Sarkar
Summary: Two homoleptic Fe(II) complexes with superbasic terpyridine derivatives as ligands were studied to investigate the relationship between spin state and electrochemical/spectroscopic behavior. Antiferromagnetic coupling between a ligand-centered radical and the high-spin metal center resulted in an anodic shift of the first reduction potential and a mixed valency species with a moderately intense intervalence-charge-transfer band. The different spin states also influenced the electrochemical reactivity, with the low-spin species acting as a precatalyst for electrocatalytic CO2 reduction and showing a Faradaic efficiency of 37% for CO formation, while the high-spin species only catalyzed proton reduction with a modest Faradaic efficiency of approximately 20%.
INORGANIC CHEMISTRY
(2023)
Article
Multidisciplinary Sciences
Zishuai Zhang, Yilong Zhu, Miao Yu, Yan Jiao, Yan Huang
Summary: Rechargeable aqueous metal parallel to I-2 electrochemical energy storage systems offer a cost-effective alternative for grid energy storage. The use of 3,4,9,10-perylenetetracarboxylic diimide (PTCDI) as a negative electrode active material and a KCl/I-2 aqueous electrolyte solution can overcome the drawbacks of metallic deposition and the formation of electrochemically inactive by-products. The proposed system shows promising performance with high discharge capacity and voltage.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Shelby L. Hooe, Juan J. Moreno, Amelia G. Reid, Emma N. Cook, Charles W. Machan
Summary: The study developed a co-electrocatalytic system using a Cr complex and DBTD as a redox mediator to achieve high efficiency and quantitative selectivity for the reduction of CO2 to CO. This assembly relies on through-space electronic conjugation between DBTD and the catalyst ligand.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Jorge Echeverria, Jesus Jover
Summary: The report explores a potential method based on a hydroboration/copper-catalyzed carboxylation reaction sequence to synthetically access fluorinated carboxylic acids. DFT calculations support the possibility of obtaining these compounds from simple fluorinated alkenes and gaseous carbon dioxide. This paves the way for the future preparation of this class of chemicals.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Ljiljana Pavlovic, Martin Pettersen, Ashot Gevorgyan, Janakiram Vaitla, Annette Bayer, Kathrin H. Hopmann
Summary: The study investigates the Rh-catalyzed hydrocarboxylation of alpha,beta-unsaturated carbonyl compounds, revealing a preference for outer-sphere CO2 insertion and an intriguing stacking interaction between CO2 and certain ligands. The experimental results support the computationally predicted low enantiomeric excesses and emphasize the challenges in developing a highly selective version of this reaction.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Multidisciplinary Sciences
Junyuan Duan, Tianyang Liu, Yinghe Zhao, Ruoou Yang, Yang Zhao, Wenbin Wang, Youwen Liu, Huiqiao Li, Yafei Li, Tianyou Zhai
Summary: This study proposes a superlattice model with alternating metal oxides and selenide sublayers, in which electrons are rapidly exported through the conductive metal selenide layer to protect the active oxide layer from self-reduction. The active [Bi2O2]2+ sublayers retain oxidation states during CO2 electroreduction due to rapid electron transfer through the conductive [Cu2Se2]2- sublayer. Theoretical calculations reveal high activity of the [Bi2O2]2+ sublayers, achieving over 90% formate selectivity. This work expands the understanding and improvement of CO2 electroreduction properties in metal oxide systems.
NATURE COMMUNICATIONS
(2022)
Review
Chemistry, Multidisciplinary
Paramita Saha, Sk Amanullah, Abhishek Dey
Summary: This article discusses the progress in the field of electrochemical CO2RR, focusing on the issue of selectivity and exploring the factors that influence selectivity. Mechanistic investigations of CO2RR, through the detection and characterization of reaction intermediates, provide a basis for developing highly selective CO2RR catalysts.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Review
Chemistry, Applied
Wanjun Sun, Jiayu Zhu, Meiyu Zhang, Xiangyu Meng, Mengxue Chen, Yu Feng, Xinlong Chen, Yong Ding
Summary: This review introduces the application of cobalt-based heterogeneous catalysts in solar-driven conversion of carbon dioxide into high value-added fuels. Strategies including extending light absorption range, promoting charge separation, providing active sites, and lowering reaction barrier are discussed to improve the photocatalytic performance. The review also outlines the applications of cobalt-based photocatalysis in CO2 reduction, water splitting, and nitrogen fixation, and presents the central challenges and possible improvements for future research.
CHINESE JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Zhibing Wen, Suxian Xu, Yong Zhu, Guoquan Liu, Hua Gao, Licheng Sun, Fei Li
Summary: In this study, a novel strategy for preparing hybrid photocathodes by immobilizing cobalt catalysts on TiO2-protected Si electrodes coated with carbon nanotubes (CNTs) is reported. The photocathodes showed high performance in reducing CO2 with a stable photocurrent density and unity Faradaic efficiency over a certain period of time.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Inorganic & Nuclear
Roman G. Belli, Victoria C. Tafuri, Nicholas A. Garcia, Courtney C. Roberts
Summary: Recently, rare earth elements have been utilized in catalyzing alkyl-alkyl cross coupling and other organic transformations. In this study, we synthesized and characterized a tris(amido) Lu complex, 1-Lu, which is similar to the Sc and Y rare earth complexes known to participate in these reactions. While 1-Lu shares similar solid state structural properties as its Group 3 congeners, EPR spectroscopy showed different behavior. Additionally, 1-Lu broke the trend of reaction rates related to oxidation potential and exhibited faster catalysis in alkyl-alkyl cross-coupling reaction compared to Sc and Y analogs. Moreover, complex 1-Lu was also demonstrated to participate in two-electron redox catalysis.
Article
Chemistry, Multidisciplinary
Senjie Ma, Christopher K. Hill, Casey L. Olen, John F. Hartwig
Summary: This study introduces a novel method for intermolecular hydroaminations of unactivated terminal alkenes catalyzed by a ruthenium complex, eliminating the need for excess alkene and providing high efficiency in producing amine products. The research suggests a new mechanism for hydroamination involving oxidative amination coupled with reduction of imine intermediates.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Biochemistry & Molecular Biology
Rodrigo A. Lemos Silva, Demetrio A. da Silva Filho, Megan E. Moberg, Ted M. Pappenfus, Daron E. Janzen
Summary: X-ray structural determinations and computational studies were used to investigate halogen interactions in two halogenated oxindoles. Comparative analyses of interaction energy and properties were carried out for different types of interactions, revealing possible pathways for intermolecular interactions through electron density and molecular electrostatic potential analyses.
Article
Chemistry, Multidisciplinary
Senjie Ma, Yumeng Xi, Haoyu Fan, Sven Roediger, John F. Hartwig
Summary: Asymmetric alkene hydroamination reactions often have limited synthetic value due to the requirement of excess alkene, limited enantioselectivity, and low tolerance towards functional groups. In this study, an enantioselective and intermolecular hydroamination reaction of unactivated terminal alkenes was developed, which occurs with equimolar amounts of alkene and amine, shows high tolerance towards functional groups, and yields products with high enantioselectivity and turnover numbers.
Article
Chemistry, Multidisciplinary
Matthew T. Whited, Wenlai Han, Helen J. Jin-Lee, Zach DiNardo, Emma Watson, Jia Zhang, Daniela Kohen
Summary: A cobalt silylene linkage enables metal/ligand cooperative activation and significantly improves the catalytic isocyanate generation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Brian Zou, Kellie A. Stellmach, Stella M. Luo, Feven L. Gebresilassie, Healeam Jung, Cathy K. Zhang, Adam D. Bass, Daron E. Janzen, Dennis D. Cao
Summary: This study demonstrates a new method for the synthesis of desirable halogenated benzene-1,2,3,4-tetracarboxylic diimide derivatives and shows that sterically challenging N-derivatizations can be achieved under microwave reactor conditions.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Review
Chemistry, Multidisciplinary
Senjie Ma, John F. Hartwig
Summary: Catalytic intermolecular hydroamination of alkenes is a valuable method for the synthesis of amines with important applications in various fields. However, achieving high yield and selectivity is challenging due to the lack of thermodynamic driving force and the occurrence of side reactions. Late transition-metal complexes have shown advantages in catalyzing hydroaminations. This Account describes the progress in catalytic hydroamination reactions catalyzed by late transition-metal complexes, including additions to activated and unactivated alkenes, and the development of enantioselective hydroaminations.
ACCOUNTS OF CHEMICAL RESEARCH
(2023)
Article
Chemistry, Multidisciplinary
Senjie Ma, Haoyu Fan, Craig S. Day, Yumeng Xi, John F. Hartwig
Summary: Remote hydrofunctionalizations of alkenes enable the incorporation of functional groups distal to carbon-carbon double bonds. This study presents a system for the remote hydroamination of disubstituted alkenes, selectively functionalizing the subterminal, unactivated, methylene position of an alkyl chain. The high regioselectivity and reaction rates are attributed to the electronic properties of the amine substituent and the ligand DIP-Ad-SEGPHOS, which was developed by considering the steric and electronic effects of ligand modules. The remote hydroamination is compatible with a diverse range of alkenes and aminopyridines, allowing for the regioconvergent synthesis of amines from isomeric mixtures of alkenes. The resulting products can be further modified through nucleophilic aromatic substitution reactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Crystallography
Daron E. Janzen, Maya S. Butler, Eric W. Reinheimer
Summary: N-benzylcinchonidinium bromide is a quaternary ammonium salt of the cinchona alkaloid cinchonidine, widely used as a chiral phase-transfer catalyst and chiral resolution agent. The study shows that both classical and non-classical hydrogen-bonding interactions, as well as anion effects, play key mechanistic roles in the catalysis of cinchona alkaloids. In order to understand the effects of water on these intermolecular interactions, the structures of anhydrous and sesquihydrate forms were determined.
ACTA CRYSTALLOGRAPHICA SECTION E-CRYSTALLOGRAPHIC COMMUNICATIONS
(2022)
Review
Chemistry, Inorganic & Nuclear
Matthew T. Whited
Summary: This Perspective summarizes the common modes of cooperativity demonstrated for pincer frameworks featuring metal/main-group bonds, highlighting similarities among boron, aluminium, and silicon donors and identifying directions for further development.
DALTON TRANSACTIONS
(2021)
Article
Crystallography
Matthew T. Whited, Margaret A. Ball, Alison Block, Benjamin A. Brewster, LouLou Ferrer, Helen J. Jin-Lee, Colby J. King, Jamie D. North, Inger L. Shelton, David G. Wilson
Summary: This article presents three cyclopentadienylmolybdenum(II) propionyl complexes with triarylphosphine ligands featuring different para substituents. These complexes exhibit similar molecular structures, with a four-legged piano-stool geometry, and are akin to related acetyl complexes. The extended structures of the complexes vary somewhat, with the para substituent of the triarylphosphine engaging in non-classical hydrogen-bonding interactions.
ACTA CRYSTALLOGRAPHICA SECTION E-CRYSTALLOGRAPHIC COMMUNICATIONS
(2021)
