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)
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
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, 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
Aziz Ullah, Guo-Qiang Chen
Summary: A metal-free one-pot 1,1,2-trifunctionalization of terminal alkynes with imines and boranes is reported. The reaction proceeds via an FLP deprotonation and alkynyl borate 1,2-migration sequence, providing a straightforward means to synthesize trisubstituted alkenyl boranes under mild conditions.
ORGANIC CHEMISTRY FRONTIERS
(2022)
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)
Review
Chemistry, Multidisciplinary
Ayan Dasgupta, Emma Richards, Rebecca L. Melen
Summary: Progress in frustrated Lewis pair (FLP) chemistry has highlighted the significance of main group elements in catalysis, introducing novel approaches to synthetic chemistry. Recent studies have uncovered new reactivities of frustrated Lewis pairs involving single-electron transfer processes, leading to the formation of reactive frustrated radical pairs (FRP). Electron Paramagnetic Resonance (EPR) spectroscopy has been employed to explain the nature and stability of the observed radical species.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Shubhajit Das, Roland C. Turnell-Ritson, Paul J. Dyson, Clemence Corminboeuf
Summary: Despite recent progress in the chemistry of frustrated Lewis pairs (FLPs), direct FLP-catalyzed hydrogenation of CO2 remains elusive. The authors propose a mapping method to link the chemical composition of FLPs with their activity in catalytic hydrogenation of CO2, and they experimentally validate a combination with high catalytic turnover.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Inorganic & Nuclear
Magdalena Siedzielnik, Kinga Kaniewska-Laskowska, Natalia Szynkiewicz, Jaroslaw Chojnacki, Rafal Grubba
Summary: A series of monoand bisaminophosphanes with unique structural features were characterized, showing short and polarized P-N bonds, pyramidal geometry at the P atom, and almost planar geometry at the N atoms. These compounds are highly nucleophilic, except for one specific structural feature, and do not react with water for the most part.
Review
Chemistry, Multidisciplinary
Pallavi Sarkar, Shubhajit Das, Swapan K. Pati
Summary: This article summarizes the progress in the study of non-boron Lewis acids since 2015, which are an important component of Frustrated Lewis pairs.
CHEMISTRY-AN ASIAN JOURNAL
(2022)
Article
Chemistry, Physical
Zhen Wan, Chengjun Wang, Chun Yang, Dongge Ma, Hongwei Ji, Chuncheng Chen, Wanhong Ma, Jincai Zhao
Summary: In this study, an unusual inverse H-transfer order is reported, where photoinduced solid In2O3-FLPs catalyze the hydrogenated dehalogenation of aryl halides. The results show that this method effectively activates the aryl halides and performs the dehalogenation reaction with high yields. By studying the H/D kinetic isotope effects and activation energies of hydrogenated dehalogenation, it is demonstrated that the initial hydride transfer mediated by photoinduced solid FLPs is more effective than common proton transfer.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2023)
Article
Chemistry, Multidisciplinary
Wei Su, Thayalan Rajeshkumar, Libo Xiang, Laurent Maron, Qing Ye
Summary: In this contribution, uranium complexes with a pendant borate or borane moiety were synthesized and investigated. Complexes 3 and 4, bearing a pendant borane group, represent the first examples of uranium complexes with a pendant borane Lewis acid. The study showed that complex 3 is capable of CO activation and abnormal CO 1,2-insertion reaction, highlighting the importance of the pendant borane moiety.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Dipendu Mandal, Ting Chen, Zheng-Wang Qu, Stefan Grimme, Douglas W. Stephan
Summary: This study investigates the properties of the products formed by the reaction between PAr3/B(C6F5)(3) and DEAD. It is found that the steric demands and electronic structures play a crucial role in determining the nature of the products.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Engineering, Environmental
Fengfeng Wang, Qijia Ding, Jinrui Ding, Yajie Bai, Hongye Bai, Weiqiang Fan
Summary: This study introduces a ZnIn2S4/BiVO4 heterostructure with zinc vacancies for efficient chemisorption and catalytic kinetics of nitrate reduction. The formation of frustrated Lewis pairs plays a critical role in enhancing the selectivity and yield rate. These findings expand the prospect of using frustrated Lewis pairs as active sites in photoelectrochemical nitrate reduction reactions.
CHEMICAL ENGINEERING JOURNAL
(2022)
Article
Chemistry, Physical
Xiaoyu Liang, Xinkui Wang, Xinxin Zhang, Sisi Lin, Min Ji, Min Wang
Summary: In this study, a ZnIn2S4/In(OH)3-x (ZIOS) heterojunction was developed for visible-light-driven CO2 reduction. The ZIOS composites, fabricated via partial sulfurization of Zn-In-O oxide, exhibit a CO formation rate of 1945.5 mu mol center dot g-1 center dot h-1, which is about 2.76-fold higher than that over ZnIn2S4, and suppress hydrogen evolution, with the CO/H2 ratio increasing from 0.436 for ZnIn2S4 to 1.6 for ZIOS. This work provides insight into the design of efficient CO2 reduction photocatalysts.