Article
Chemistry, Physical
Ranita Pal, Manas Ghara, Pratim Kumar Chattaraj
Summary: This article provides a review of the chemistry of frustrated Lewis pair (FLP) in the activation of small molecules, hydrogenation of CO2, and unsaturated organic species. Experimental works and electronic structure theory calculations are used to gain mechanistic insights into the reactivity of FLPs. The findings can guide the design of more efficient FLP catalysts for hydrogen activation.
Review
Chemistry, Multidisciplinary
Minsoo Ju, Zhipeng Lu, Luiz F. T. Novaes, Jesus I. Martinez Alvarado, Song Lin
Summary: Frustrated radical pairs (FRPs) are able to coexist in solution due to steric repulsion or weak bonding association between two distinct radicals, which would otherwise annihilate each other. They are typically formed via spontaneous single-electron transfer between two sterically encumbered precursors and exhibit orthogonal chemical properties. FRPs have been found to be capable of homolytically activating various chemical bonds and are being extensively explored in synthetic organic chemistry, including C-H bond functionalization.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Christoph Wallach, Felix S. Geitner, Antti J. Karttunen, Thomas F. Faessler
Summary: The unique three-dimensional structure of spherical, homoatomic nine-atom germanium clusters allows for various spatial arrangement of functional groups. Recent introduction of ligands with lone pairs and addition of boranyl group to the cluster featuring a Ge-B exo-cluster bond have expanded the possibilities in cluster chemistry. Quantum-chemical calculations have revealed the frustrated Lewis pair character of the boranyl-functionalized cluster.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Haishuai Cui, Xiaoqing Liao, Yufan Ren, Yang Zhou, Jing Xiao, Renjie Deng, Yang Lv, Huajie Liu, Pingle Liu, Hai Yang
Summary: In this article, a facile strategy is proposed to synthesize oxygen-defect-rich Co3O4@NC porous nanorods. These materials are proven to have FLPs sites. The oxygen-defect-rich Co3O4@NC exhibits high selectivity and catalytic performance towards cinnamaldehyde.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Physical
Hui Mao, Zijiang Chen, Longjiu Cheng, Kun Wang
Summary: The article discusses the catalytic effect and hydrogen storage potential of Frustrated Lewis Pairs (FLPs) in the hydrogenation process, emphasizing the influence of acidity and alkalinity on the activity and reversibility of FLPs. The study found that FLPs composed of strong acids and relatively weak bases exhibit better reversibility and reaction rates in hydrogenation.
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
(2021)
Review
Biochemical Research Methods
Gitanjali Sharma, Paul D. Newman, James A. Platts
Summary: This review discusses the power of quantum chemistry, particularly density functional theory (DFT), in unraveling mechanisms in the field of FLP chemistry. It covers various aspects such as hydrogen activation, borylation, silylation, polymerization, formation of heterocycles, reaction with small gaseous molecules, alkenes, terminal alkynes, and the role of DFT in understanding regio-selectivity, steric effects, London dispersion, and covalent interactions in FLPs.
JOURNAL OF MOLECULAR GRAPHICS & MODELLING
(2021)
Article
Chemistry, Multidisciplinary
Wenwen Lin, Hao Chen, Gaobo Lin, Siyu Yao, Zihao Zhang, Jizhen Qi, Meizan Jing, Weiyu Song, Jing Li, Xi Liu, Jie Fu, Sheng Dai
Summary: In this study, a defective boron carbon nitride catalyst was developed, which achieved high Faraday efficiency and ammonia yield, and had long-term durability.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Biochemistry & Molecular Biology
Qiang Wan, Sen Lin, Hua Guo
Summary: This article reviews recent theoretical advances in understanding FLP-based heterogeneous catalysis in various applications, such as metal oxides, functionalized surfaces, and two-dimensional materials. It emphasizes the importance of a better understanding of the catalytic mechanism for the experimental design of novel heterogeneous FLP catalysts.
Article
Chemistry, Multidisciplinary
Yan Liang, Zhong Zhang, Xiaofang Su, Xiao Feng, Songzhu Xing, Wei Liu, Rui Huang, Yiwei Liu
Summary: Precisely controlling the structure and spatial distance between Lewis acid and Lewis base sites in a porous system is essential for constructing efficient solid frustrated Lewis pair (FLP) catalysts. In this study, FLP sites were constructed in a polyoxometalate (POM)-based metal-organic framework (MOF) by introducing coordination-defect metal nodes (Lewis acid) and surface-basic POM with abundant oxygen (Lewis base). The resulting FLP catalyst exhibited high hydrogenation activity, with 55 and 2.7 times higher activity compared to defect-free POM-based MOF and defective MOF without POM, respectively. This work offers a new approach for the precise design of multi-site catalysts for specific substrate activation and synergistic catalysis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Huaxun Luo, Boyu Zhu, Xiaomin Liu, Xiaomin Zhang, Tianxiang Zhao, Xingbang Hu
Summary: Through experimental and computational studies, it was found that moderately bulky bases can activate hydrogen and serve as catalysts for the hydrogenation of CO2 to formate. Typical frustrated Lewis pairs (FLPs), known for their high efficiency in H2 activation, were found to be less efficient than non-frustrated Lewis pairs (n-FLPs) for this reaction. These results are expected to inspire the development of novel Lewis pair catalyzed reactions.
MOLECULAR CATALYSIS
(2023)
Article
Multidisciplinary Sciences
Zhipeng Lu, Minsoo Ju, Yi Wang, Jonathan M. Meinhardt, Jesus I. Martinez Alvarado, Elisia Villemure, Jack A. Terrett, Song Lin
Summary: This study demonstrates the functionalization of C(sp(3))-H bonds using frustrated radical pairs (FRPs) generated from disilazide donors and an N-oxoammonium acceptor. The FRPs cleave unactivated C-H bonds to provide aminoxylated products, and the reaction selectivity towards tertiary, secondary, or primary C-H bonds can be controlled by tuning the structure of the donor. Mechanistic studies confirm the formation and involvement of radical pairs in the target reaction.
Article
Chemistry, Physical
Yong Zou, Mingkai Zhang, Yuxuan Liu, Yuanyuan Ma, Sai Zhang, Yongquan Qu
Summary: Interfacial frustrated Lewis pairs constructed on the CeO2 surface have been demonstrated as novel catalytic active sites for highly selective transfer hydrogenation, showing great potential for the conversion of biomass.
JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Inorganic & Nuclear
Shubhajit Das, Swapan K. Pati
Summary: This study investigates a family of intramolecular stannylium/nitrogen FLPs for catalytic hydrogenation of organic compounds with unsaturated functional groups. The activation of H-2 by these FLPs proceeds through the cooperative action of the Sn and N centers, allowing for catalytic hydrogenation of organic substrates. The reactivity of these FLPs can be tuned by varying substituents and counter anions on the Sn center.
Article
Chemistry, Physical
Panpan Wu, Hui Mao, Zijiang Chen, Longjiu Cheng, Kun Wang
Summary: In this study, Frustrated Lewis pairs (FLPs) with different acidity/basicity were selected and designed. It was found that FLPs composed of soft strong Lewis acid (LA) and hard moderate Lewis base (LB) showed the best activity and reversibility in hydrogenation. The cooperativity between LA and LB was demonstrated to determine the catalytic performance in hydrogen activation.
Article
Engineering, Environmental
Meng Jiang, Yuxiang Zhu, Xiang Zhong, Qiufan Sun, Shengshen Gu, Jianfeng Yao
Summary: A three-dimensional boron-doped carbon nitride catalyst with high electrocatalytic nitrogen reduction reaction activity is reported in this study for ammonia production. The optimized doping content and unique 3D structure of the catalyst enhance the contact between electrolyte and active sites, improve nitrogen adsorption and activation, and lower the barrier for nitrogen reduction reaction. This research opens up a new avenue for the rational design of nonmetal-based catalysts for nitrogen reduction.
CHEMICAL ENGINEERING JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Daniel Kohs, Jonathan Becker, Hermann A. Wegner
Summary: In this study, a modular synthesis method was reported for the preparation of substituted cycloparaphenylenes (CPPs) of different sizes. By using a specific compound, the ring size of the final product can be conveniently controlled. Substituted nanohoops were successfully synthesized through a simple reaction and exhibited a tightly packed tube-like arrangement in the crystal structure.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Thomas C. Schaefer, Jonathan Becker, Marcel T. Seuffert, Dominik Heuler, Alexander E. Sedykh, Klaus Mueller-Buschbaum
Summary: Eight cationic, two-dimensional metal-organic frameworks were synthesized using group 13 metal halides and dipyridyl ligands. These frameworks can capture iodine molecules at room temperature and additional coordination polymers and complexes were also identified in the reactions.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Max Hasenbeck, Tizian Muller, Arthur Averdunk, Jonathan Becker, Urs Gellrich
Summary: In this study, the reaction of Piers' borane with arylacetylenes was shown to lead to the diastereoselective formation of boryl-substituted tetra-aryl-tetrahydropentalenes through a series of 1,2-carboboration reactions and subsequent rearrangements. Isotope labeling experiments and DFT computations provided insights into the reaction mechanism, revealing a complex pathway involving multiple carbon-carbon bond formations.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Felix Wech, Urs Gellrich
Summary: This review discusses the hydrogenation of organic substrates catalyzed by borane-based frustrated Lewis pairs, with a focus on the mechanistic aspects of these catalytic reactions.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Multidisciplinary
Arthur Averdunk, Max Hasenbeck, Tizian Mueller, Jonathan Becker, Urs Gellrich
Summary: A novel method for the coupling of unactivated alkynes and arylallenes has been reported, which involves the regioselective 1,2-carboboration of the allene by an alkenylborane. The resulting boryl-substituted 1,4-dienes are suitable for a subsequent Suzuki-Miyaura coupling with aryl iodides, allowing for the synthesis of aryl-substituted 1,4-dienes in a three-step, one-pot protocol. The generality of the reaction was demonstrated by the synthesis of twenty dienes with modular variations.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Peter R. Schreiner, Lars Rummel, Kai Hanke, Jonathan Becker
Summary: In this study, the thermodynamic stability of cis- and trans-alkenes substituted with dispersion energy donor (DED) groups was investigated through a combination of experimental and computational methods. The equilibrium between the two isomers was found to shift towards the more crowded cis-alkene as the substituent size increased. Noncovalent interactions, particularly long-range dispersion (LD) and Pauli exchange repulsion, were identified as the dominant factors influencing the equilibrium between cis- and trans-alkenes.
Article
Chemistry, Inorganic & Nuclear
Thomas Rotaermel, Pascal Specht, Jonathan Becker, Adam Neuba, Siegfried Schindler
Summary: In the active site of copper monooxygenases, thioether residues coordinate through the sulfur atom. The reaction between dioxygen and copper(I) complexes with thioether groups was investigated, and the formation of labile intermediates and copper(II) complexes was detected. The finding of increased stability in the formed superoxido copper complex by replacing the ethyl group with a methyl group in a specific derivative was particularly interesting. Ozone measurements were conducted to explore alternative ways to obtain and stabilize labile intermediates.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Heba Youssef, Jonathan Becker, Alexander E. Sedykh, Thomas Schaefer, Ilya Taydakov, Klaus Mueller-Buschbaum
Summary: A series of lanthanide and alkaline earth metal complexes were synthesized using organic synthesis methods, and their thermal stability and luminescent properties were investigated. The Ce3+ compound exhibited a bright red emission color, and co-doping of Gd-containing complexes with Eu3+ and Tb3+ allowed for tuning of the emission color.
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE
(2022)
Article
Chemistry, Inorganic & Nuclear
Tizian Mueller, Max Hasenbeck, Jonathan Becker, Urs Gellrich
Summary: The formation of bridged boracycle 1 was reported through the reaction between cyclooctatetraene and bis(pentafluorophenyl)borane. Computational studies revealed that the reaction begins with a hydroboration and is followed by a rearrangement induced by the high Lewis acidity of bis(pentafluorophenyl)borane, resulting in the cleavage of a carbon-carbon bond via a nonclassical zwitterion and a final 1,1-carboboration. An intermediate of the reaction was observed as a tri-tert-butylphosphine adduct.
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE
(2023)
Article
Chemistry, Organic
Ravindra S. Phatake, Tizian Mueller, Arthur Averdunk, Urs Gellrich
Summary: We have discovered a bis(pentafluorophenyl)borane-catalyzed isomerization reaction that selectively converts terminal alkenes to internal alkenes. This transformation can be achieved under mild reaction conditions and with low catalyst loadings. Interestingly, our method also allows for long-range isomerization of aryl alkenes. We have investigated the reaction mechanism using dispersion-corrected spin-component scaled double hybrid DFT computations, revealing a hydroboration/retro-hydroboration sequence.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Heba Youssef, Jonathan Becker, Clemens Pietzonka, Ilya V. Taydakov, Florian Kraus, Klaus Mueller-Buschbaum
Summary: The redox reactions between lanthanide metals and 3-(4-pyridyl)pyrazole or 3-(3-pyridyl)pyrazole ligands produced various coordination polymers with different luminescent properties. The ligands 3-PyPz(-) and 4-PyPz(-) were found to be effective antennas for lanthanide-based luminescence in the visible and near-infrared range. The magnetic studies showed magnetic isolation of lanthanide centers in certain crystal lattices.
CHEMISTRY-SWITZERLAND
(2023)
Article
Multidisciplinary Sciences
Satoshi Takebayashi, Jama Ariai, Urs Gellrich, Sergey V. Kartashov, Robert R. Fayzullin, Hyung-Been Kang, Takeshi Yamane, Kenji Sugisaki, Kazunobu Sato
Summary: Metallocenes, versatile organometallic compounds, can stabilize a wide range of formal electron counts. While d-block metallocenes with up to 20 electron counts have been synthesized and utilized, those with more than 20 counts have remained elusive and challenging to synthesize and isolate. In this study, a 21-electron cobaltocene derivative was successfully synthesized, isolated, and characterized, expanding our understanding of d-block metallocene chemistry.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Jama Ariai, Urs Gellrich
Summary: This article presents a systematic study on the entropic penalty for associative reactions and identifies that computed solution-phase Gibbs free energies tend to overestimate entropic contributions. An additive correction scheme based on Garza's formalism is proposed to correct the entropic penalty, which is suitable for routine applications by non-expert users.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Materials Science, Multidisciplinary
Morteza Aghaee, Arun Akkala, Zulfi Alam, Rizwan Ali, Alejandro Alcaraz Ramirez, Mariusz Andrzejczuk, Andrey E. Antipov, Pavel Aseev, Mikhail Astafev, Bela Bauer, Jonathan Becker, Srini Boddapati, Frenk Boekhout, Jouri Bommer, Tom Bosma, Leo Bourdet, Samuel Boutin, Philippe Caroff, Lucas Casparis, Maja Cassidy, Sohail Chatoor, Anna Wulf Christensen, Noah Clay, William S. Cole, Fabiano Corsetti, Ajuan Cui, Paschalis Dalampiras, Anand Dokania, Gijs de Lange, Michiel de Moor, Juan Carlos Estrada Saldana, Saeed Fallahi, Zahra Heidarnia Fathabad, John Gamble, Geoff Gardner, Deshan Govender, Flavio Griggio, Ruben Grigoryan, Sergei Gronin, Jan Gukelberger, Esben Bork Hansen, Sebastian Heedt, Jesus Herranz Zamorano, Samantha Ho, Ulrik Laurens Holgaard, Henrik Ingerslev, Linda Johansson, Jeffrey Jones, Ray Kallaher, Farhad Karimi, Torsten Karzig, Cameron King, Maren Elisabeth Kloster, Christina Knapp, Dariusz Kocon, Jonne Koski, Pasi Kostamo, Peter Krogstrup, Mahesh Kumar, Tom Laeven, Thorvald Larsen, Kongyi Li, Tyler Lindemann, Julie Love, Roman Lutchyn, Morten Hannibal Madsen, Michael Manfra, Signe Markussen, Esteban Martinez, Robert McNeil, Elvedin Memisevic, Trevor Morgan, Andrew Mullally, Chetan Nayak, Jens Nielsen, William Hvidtfelt Padkaer Nielsen, Bas Nijholt, Anne Nurmohamed, Eoin OFarrell, Keita Otani, Sebastian Pauka, Karl Petersson, Luca Petit, Dmitry I. Pikulin, Frank Preiss, Marina Quintero-Perez, Mohana Rajpalke, Katrine Rasmussen, Davydas Razmadze, Outi Reentila, David Reilly, Richard Rouse, Ivan Sadovskyy, Lauri Sainiemi, Sydney Schreppler, Vadim Sidorkin, Amrita Singh, Shilpi Singh, Sarat Sinha, Patrick Sohr, Tomas Stankevic, Lieuwe Stek, Henri Suominen, Judith Suter, Vicky Svidenko, Sam Teicher, Mine Temuerhan, Nivetha Thiyagarajah, Raj Tholapi, Mason Thomas, Emily Toomey, Shivendra Upadhyay, Ivan Urban, Saulius Vaitiekenas, Kevin Van Hoogdalem, David Van Woerkom, Dmitrii V. Viazmitinov, Dominik Vogel, Steven Waddy, John Watson, Joseph Weston, Georg W. Winkler, Chung Kai Yang, Sean Yau, Daniel Yi, Emrah Yucelen, Alex Webster, Ruichen Zhao
Summary: In this study, measurements and simulations of semiconductor-superconductor heterostructure devices were conducted to observe topological superconductivity and Majorana zero modes. The devices were optimized to ensure robustness against nonuniformity and disorder. Experimental results indicate the presence of a topological superconducting phase, which is a prerequisite for experiments involving Majorana zero modes fusion and braiding.
Article
Chemistry, Multidisciplinary
Thomas C. Schaefer, Jonathan Becker, Dominik Heuler, Marcel T. Seuffert, Alexander E. Sedykh, Klaus Mueller-Buschbaum
Summary: Four structurally closely related one-dimensional coordination polymers (CPs) with different metal halides were synthesized and characterized. Unprecedented coordination geometries were observed in two of the complexes.
AUSTRALIAN JOURNAL OF CHEMISTRY
(2022)
