Article
Chemistry, Physical
Li-Ming Zhang, Wenjun Luo, Jiangzhen Fu, Yu Liu, Junliang Zhang
Summary: A newly developed PNP-type W-Phos ligand showed a unique effect on the catalytic asymmetric addition of reactive Grignard reagents to ketimines. This enabled a Cu(I)-catalyzed asymmetric alkylation reaction of N-sulfonyl ketimines, resulting in the formation of optically active α-tertiary amines with high enantioselectivities.
Article
Chemistry, Physical
Xin-Shen Liang, Rui-Dong Li, Wei Sun, Zhong Liu, Xiao-Chen Wang
Summary: Borane-mediated hydride abstraction has been shown to be a powerful tool for the C(sp(3))-H functionalization of amines, but its activity with ethers is still unknown. In this study, we discovered this activity in 2H-chromenes and established a catalytic C(sp(3))-H functionalization reaction using silyl ketene acetals as nucleophiles.
Article
Chemistry, Multidisciplinary
Nian Xu, Maoping Pu, Han Yu, Gaofei Yang, Xiaohua Liu, Xiaoming Feng
Summary: This study achieved the direct alpha-alkylation of acyclic carbonyls with nonactivated hydrocarbons using iron-based catalysts, resulting in highly selective products. The use of a chiral iron complex and oxidants allowed for the high enantioselectivity (up to 99% ee) with good compatibility in yields (up to 88%).
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Xiang-Lei Han, Bin Hu, Chao Fei, Zhe Li, Yang Yu, Cheng Cheng, Bruce Foxman, Jisheng Luo, Li Deng
Summary: This study reports an unprecedented catalytic asymmetric cross-coupling reaction that allows a variety of ketimines and aldimines to react, resulting in the direct synthesis of chiral vicinal diamines. This reaction is enabled by the development of a new chiral ammonium catalyst, which leads to highly diastereo- and enantioselective formation of diverse chiral vicinal diamines. It establishes a new approach for the asymmetric synthesis of chiral vicinal diamines.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Review
Chemistry, Organic
C. M. A. Afsina, Thaipparambil Aneeja, Mohan Neetha, Gopinathan Anilkumar
Summary: Copper-catalyzed organic reactions have attracted widespread attention due to the abundance and affordability of copper, as well as its low toxicity, eco-friendliness, sustainable nature, and versatility as a catalyst. These reactions are primarily used for the synthesis of biologically important nitrogen heterocycles, amines, amides, imines, and alkynes.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Cristian Cavedon, Sebastian Gisbertz, Susanne Reischauer, Sarah Vogl, Eric Sperlich, John H. Burke, Rachel F. Wallick, Stefanie Schrottke, Wei-Hsin Hsu, Lucia Anghileri, Yannik Pfeifer, Noah Richter, Christian Teutloff, Henrike Mueller-Werkmeister, Dario Cambie, Peter H. Seeberger, Josh Vura-Weis, Renske M. van der Veen, Arne Thomas, Bartholomaus Pieber
Summary: We demonstrate visible-light-mediated carbon-heteroatom cross-coupling reactions using a photoactive Ni(II) precatalyst. The activation of this precatalyst involves an initial intraligand charge transfer event triggered by visible light irradiation. Additionally, a porous, recyclable organic polymer for heterogeneous nickel catalysis of cross-coupling reactions is obtained through ligand polymerization.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
James E. Baumann, Gojko Lalic
Summary: A new method for the differential dihydrofunctionalization of terminal alkynes has been developed, enabling the synthesis of allylic boronate esters through a reductive three-component coupling reaction. This transformation, promoted by a copper/palladium catalyst system, hydrofunctionalizes both pi-bonds of the alkyne. The method is compatible with a wide range of functional groups.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Zi-Tong Pan, Xu-Kuan Qi, Qian Xiao, Xi-Wen Liang, Jian-Ji Zhong, Jing-Xin Jian, Qing-Xiao Tong
Summary: In this study, we have demonstrated a regulable cross-coupling reaction using alcohols as alkylating reagents to functionalize benzothiazoles. We obtained two types of cross-coupling products with high isolated yields, opening up a broad research prospect for expanding alcohols as alkylating reagents.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Alexander Reichle, Magdalena Koch, Hannes Sterzel, Lea-Joy Grosskopf, Johannes Floss, Julia Rehbein, Oliver Reiser
Summary: The visible light-mediated copper-catalyzed vicinal difunctionalization of olefins utilizing bromonitroalkanes as ATRA reagents is reported. This method offers high yields, fast reaction times, and environmentally benign reaction conditions with a wide scope, allowing rapid functionalization of activated and unactivated olefins. Additionally, it demonstrates the late-stage functionalization of biologically active molecules and the upscaling to gram quantities, providing possibilities for further transformations such as the preparation of nitro- and aminocyclopropanes. Moreover, this study highlights the unique role of copper in photoredox catalysis by stabilizing and interacting with radical intermediates in its coordination sphere, as revealed by EPR studies that show its superior performance compared to iridium-based photocatalysts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Huan Zhou, Zhong-Liang Li, Qiang-Shuai Gu, Xin-Yuan Liu
Summary: Transition-metal-catalyzed asymmetric C-(sp(3))-C cross-coupling is an efficient method for the rapid synthesis of enantioenriched molecules. Chiral copper catalysts have been designed to promote a variety of asymmetric radical C(sp(3))-C cross-coupling reactions with high efficiency and enantioselectivity. The key to success lies in the design of chiral ligands to initiate the reaction and achieve enantiocontrol over the highly reactive prochiral alkyl radical species.
Review
Chemistry, Inorganic & Nuclear
Prensha Arora, Parveen Kumar, Vijesh Tomar, Mika Sillanpaa, Raj Kumar Joshi, Meena Nemiwal
Summary: Molecules containing nitrogen play a crucial role in synthetic chemistry. The Cu-catalyzed cross-coupling reactions that create C-N bonds are an important method for synthesizing anilines and aniline derivatives. The use of nanomaterials catalysis in C-N coupling reactions is attracting great attention due to its greener approach. This review provides a comprehensive overview of the copper oxide nanoparticles catalyzed C-N bond formation.
INORGANIC CHEMISTRY COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Shuaipeng Lv, Qiannan Li, Ji-Wei Sang, Yu Zhang, Jinxin Wang, Wei-Dong Zhang
Summary: A homogeneous photocatalytic system for the selective radical-radical cross-coupling of N-substituted amines and indoles has been developed. This system can work in water or acetonitrile, and the uranyl nitrate can be reused as the photocatalyst via simple extraction. By using this mild strategy, good to excellent yields of cross-coupling products can be achieved, even under sunlight irradiation. The proposed radical-radical cross-coupling mechanism is supported by experimental evidence and previous literature. The feasibility of this strategy has been demonstrated through gram-scale synthesis.
Article
Chemistry, Multidisciplinary
Daniels Posevins, Aitor Bermejo-Lopez, Jan-E. Backvall
Summary: An iron-catalyzed cross-coupling reaction of propargyl ethers with Grignard reagents was disclosed, allowing for efficient chirality transfer and preparation of various fluoroalkyl allenes. Additionally, an iron-catalyzed cross-coupling of Grignard reagents with alpha-alkynyl oxetanes and tetrahydrofurans was demonstrated as a straightforward approach towards fully substituted beta- or gamma-allenols.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Feixiang Sun, Jiamin Huang, Zhihong Wei, Conghui Tang, Weiping Liu
Summary: A homogeneous manganese-catalyzed cross-coupling reaction of secondary alcohols was developed for the synthesis of gamma-disubstituted alcohols and beta-disubstituted ketones. The protocol, using Mn-MACHO(Ph) as the catalyst, exhibited a wide substrate scope and good functional group tolerance, resulting in diverse valuable disubstituted alcohols and ketones in moderate to good yields. The selective formation of alcohol products was found to be influenced by reaction temperature, with alcohols favored over ketones at lower temperatures.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Saidkhodzha Nematulloev, Arunachalam Sagadevan, Badriah Alamer, Aleksander Shkurenko, Renwu Huang, Jun Yin, Chunwei Dong, Peng Yuan, Khursand E. Yorov, Azimet A. Karluk, Wasim J. Mir, Bashir E. Hasanov, Mohamed Nejib Hedhili, Naveen M. Halappa, Mohamed Eddaoudi, Omar F. Mohammed, Magnus Rueping, Osman M. Bakr
Summary: This study reports the synthesis of atomically precise copper hydride nanoclusters with a controlled defect, which were demonstrated to be highly selective catalysts for C-C cross-couplings. The work highlights the potential of defective nanoclusters as model systems for investigating individual defects, correlating defects with physicochemical properties, and rationally designing new nanoparticle catalysts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Multidisciplinary
Zongyan Gao, Israel Temprano, Jiang Lei, Linbin Tang, Junjian Li, Clare P. Grey, Tao Liu
Summary: This article reviews the development of LiOH-based nonaqueous lithium-air batteries (LABs). Various catalytic systems that can activate LiOH-based electrochemistry are compared, with a focus on the oxygen reduction and evolution reactions in nonaqueous media. Key factors that can switch the cell chemistry between Li2O2 and LiOH are identified, and the debate and potential causes for opposing opinions are discussed.
ADVANCED MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Miyeon Chang, Wenhao Ren, Weiyan Ni, Seunghwa Lee, Xile Hu
Summary: In this study, the effects of three different ionomers (Nafion, Sustainion-type XA-9, and poly(terphenyl piperidinium) (PTP)) on the electrochemical reduction of CO2 using Cu-based electrocatalysts were investigated. It was found that Nafion had little influence on the performance, XA-9 promoted CO formation, and PTP favored hydrogen and formate production. The observed effects were attributed to charge transfer and hydrophilicity/hydrophobicity of the ionomers. This study highlights the structure-sensitive nature of the ionomer-catalyst interaction in CO2RR.
Article
Chemistry, Multidisciplinary
Angela F. F. Harper, Steffen P. P. Emge, Pieter C. M. M. Magusin, Clare P. P. Grey, Andrew J. J. Morris
Summary: Understanding the electronic structure of materials is vital for the development of functional devices such as semiconductors, solar cells, and Li-ion batteries. However, the disorder in atomic arrangement poses challenges in determining the structure and properties of amorphous materials. In this study, we propose a method to develop amorphous models by combining experimental techniques like solid-state NMR and XAS with ab initio molecular dynamics simulations. We apply this method to amorphous alumina and successfully predict its atomic arrangement and electronic density of states. This work represents a significant advancement in the field of solid-state amorphous modeling.
Article
Chemistry, Physical
Teresa Insinna, Euan N. Bassey, Katharina Marker, Alberto Collauto, Anne-Laure Barra, Clare P. Grey
Summary: Graphite is a highly suitable anode material for lithium-ion batteries due to its low cost, low toxicity, and abundance. This study utilized electron paramagnetic resonance (EPR) spectroscopy to investigate the electronic structures of lithiated graphite anodes at different states of lithiation. The results demonstrated the heterogeneity within graphite particles and the presence of hyperfine coupling to lithium nuclei, highlighting the power of EPR spectroscopy in characterizing the local electronic structure of graphite and paving the way for its use in screening and investigating novel materials for lithium-ion batteries.
CHEMISTRY OF MATERIALS
(2023)
Article
Chemistry, Physical
Sundeep Vema, Farheen N. Sayed, Supreeth Nagendran, Burcu Karagoz, Christian Sternemann, Michael Paulus, Georg Held, Clare P. Grey
Summary: Garnet solid-electrolyte-based Li-metal batteries have the potential to be used in high-energy density and thermally stable energy storage devices. However, the formation of lithium hydroxide and carbonate on the garnet surface in an ambient atmosphere poses processing challenges. This study investigates the decomposition of surface layers under different gas environments and identifies that heating under an oxygen atmosphere leads to a clean garnet surface, while low oxygen partial pressures result in additional carbon deposits. The clean garnet surface reacts with moisture and carbon dioxide, indicating a need for control over CO2 concentration during garnet handling. Symmetric cells with low interface resistance and dendrite-free plating currents are achieved by heating under O₂ and avoiding H₂O and CO₂.
ACS ENERGY LETTERS
(2023)
Article
Chemistry, Physical
Adam J. Lovett, Venkateswarlu Daramalla, Farheen N. Sayed, Debasis Nayak, Muireann de h-Ora, Clare P. Grey, Sian E. Dutton, Judith L. MacManus-Driscoll
Summary: Epitaxial cathodes in lithium-ion microbatteries are ideal model systems for studying mass and charge transfer across interfaces and degradation processes. In this study, we report the growth of epitaxial LiMn2O4 (LMO) thin films on a new current collector material, NiCo2O4 (NCO), at a low temperature of 360°C. Our films show a discharge capacity of >100 mAh g(-1) for >6000 cycles, indicating long-term electrochemical stability of our NCO current collector. This research offers a route towards high-performance microbatteries for miniaturized electronic devices.
ACS ENERGY LETTERS
(2023)
Article
Chemistry, Physical
Arvind Pujari, Byung-Man Kim, Farheen N. Sayed, Kate Sanders, Wesley M. Dose, Angus Mathieson, Clare P. Grey, Neil C. Greenham, Michael De Volder
Summary: Light-rechargeable photobatteries are a solution to the intermittency of solar irradiation. This study analyzes the thermal contributions to the increase in capacity of two promising photoactive cathode materials under different charging conditions. The results show that the increase in capacity is mainly due to thermal effects.
ACS ENERGY LETTERS
(2023)
Article
Chemistry, Physical
Ioan-Bogdan Magdau, Daniel J. Arismendi-Arrieta, Holly E. Smith, Clare P. Grey, Kersti Hermansson, Gabor Csanyi
Summary: In this study, a powerful machine learning approach is presented for simulating the molecular behavior of the EC:EMC binary solvent in liquid electrolytes. This method accurately captures the key properties of the organic molecule mixture and addresses the challenge of scale separation between intra- and inter-molecular interactions in condensed phase molecular systems.
NPJ COMPUTATIONAL MATERIALS
(2023)
Article
Chemistry, Physical
Weiyan Ni, Josephine Lederballe Meibom, Noor Ul Hassan, Miyeon Chang, You-Chiuan Chu, Anna Krammer, Songlan Sun, Yiwei Zheng, Lichen Bai, Wenchao Ma, Seunghwa Lee, Seongmin Jin, Jeremy S. Luterbacher, Andreas Schuler, Hao Ming Chen, William E. Mustain, Xile Hu
Summary: Hydroxide exchange membrane fuel cells (HEMFCs) are promising devices for energy conversion. Now, a porous nitrogen-doped carbon-supported PtRu catalyst for the hydrogen oxidation reaction is presented, consisting of Pt single atoms and PtRu nanoparticles that work synergistically. The catalyst enables a fuel cell that exceeds the US Department of Energy 2022 performance target.
Article
Chemistry, Physical
Annalena R. Genreith-Schriever, Hrishit Banerjee, Ashok S. Menon, Euan N. Bassey, Louis F. J. Piper, Clare P. Grey, Andrew J. Morris
Summary: Ni-rich lithium-ion cathode materials exhibit high voltages and capacities, but face issues of structural instability and oxygen loss. The instability arises from the oxidation of oxygen during delithiation, with nickel displaying a charge state of approximately +2 and oxygen varying between -2 (NiO), -1.5 (LiNiO2), and -1 (NiO2). Computational calculations and X-ray spectroscopy demonstrate agreement with experimental spectra. Molecular dynamics simulations reveal oxygen loss from the (012) surface of delithiated LiNiO2, resulting in the formation of peroxide ions and subsequent oxidation to oxygen gas.
Article
Chemistry, Physical
Wenhao Ren, Wenchao Ma, Xile Hu
Summary: Electrochemical CO reduction can be used to efficiently convert CO2 to chemical fuels. However, current membrane electrode assembly (MEA) CO electrolyzers suffer from low energy efficiency. This study shows that the transport of water and hydroxide ions at the quasi-two-phase interface of the cathode limits the performance of MEA electrolyzers at high current densities. By improving interfacial mass transport, the researchers achieved a lower cell voltage, higher stability, and higher Faradaic yield.
Article
Materials Science, Multidisciplinary
Hrishit Banerjee, Clare P. Grey, Andrew J. Morris
Summary: Using ab initio dynamical mean-field theory, this study explores the electronic and magnetic states of layered LixMnO2 as a function of x, the state-of-charge. The results show different states of the system during delithiation at various charge states, and the presence of high-spin state is observed to be most likely.
Article
Chemistry, Physical
Svetlana Menkin, Jana B. Fritzke, Rebecca Larner, Cas de Leeuw, Yoonseong Choi, Anna B. Gunnarsdottir, Clare P. Grey
Summary: This study reveals the presence of soft shorts, which are often overlooked due to their indistinguishable electrochemical signatures, in realistic conditions using impedance spectroscopy and operando NMR. It also demonstrates the predictability of soft shorts and the potential use of electrochemical impedance spectroscopy for early detection of catastrophic shorts and battery failure.
FARADAY DISCUSSIONS
(2023)
Article
Chemistry, Physical
Erlendur Jonsson, Astrid H. Berge, Clare P. Grey, Israel Temprano
Summary: In this study, the role of electrolyte composition in the solvation of I- in iodide-based redox mediation in Li-O-2 batteries was investigated using a molecular dynamics approach. The results showed that shorter glymes allow for a closer packing of I- redox mediator, and increasing the concentration of I- reduces the solvation of Li+ in glymes. The presence of water further facilitates the interaction between I- and Li+, with a more pronounced effect in monoglyme. The competition between Li+ and I- for water coordination is modulated by different solvents, with longer chain lengths being less affected by increases in water concentrations.
FARADAY DISCUSSIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Rosa Muller, Olivia Georghiades, Joshua D. Bocarsly, Farheen N. Sayed, Victor Riesgo-Gonzalez, Andrew D. Bond, Clare P. Grey, Dominic S. Wright
Summary: This study investigates the potential of lanthanide-containing polyoxotitanates as single-source precursors for hybrid oxides. The properties of the compounds were characterized using magnetic measurements, and their stability at high temperatures was observed.
DALTON TRANSACTIONS
(2023)
