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, Multidisciplinary
Yin Zhang, Songbo Chen, Abdullah M. Al-Enizi, Ayman Nafady, Zhiyong Tang, Shengqian Ma
Summary: In this study, a strategy for integrating molecular chiral frustrated Lewis pair (CFLP) with porous metal-organic framework (MOF) was proposed and the catalyst CFLP@MOF was successfully constructed, which enables heterogeneous asymmetric hydrogenation. The developed CFLP@MOF catalyst exhibits high activity/enantio-selectivity and excellent recyclability/regenerability, providing a new avenue for the design and preparation of advanced catalysts for asymmetric catalysis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
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, Organic
Qiang Liu, Liu Yang, Chenfei Yao, Jiao Geng, Youting Wu, Xingbang Hu
Summary: Two strategies were reported to prevent the deactivation of Frustrated Lewis pairs (FLPs) in the hydrogenation of terminal alkynes: reducing the Lewis acidity and polymerizing the Lewis acid. A polymeric Lewis acid (P-BPh3) with high stability was designed and synthesized, leading to excellent conversion and selectivity in the hydrogenation of terminal alkynes. This catalytic system works well for different substrates, and the P-BPh3 can be easily recycled.
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
Amarajothi Dhakshinamoorthy, Abdullah M. Asiri, Hermenegildo Garcia
Summary: This article discusses the potential of metal-organic frameworks (MOFs) in heterogeneous catalysis as frustrated Lewis acid-base pairs (FLPs) or bifunctional acid-base solid catalysts for activating molecular hydrogen. Specifically, it focuses on the use of MOFs as Lewis acid and Lewis base catalysts, and the efforts to heterogenize boron and amine in MOFs to mimic molecular FLP systems. The article highlights the catalytic hydrogenation capabilities of UiO-66 and MIL-101 MOFs and their significance in selectively hydrogenating polar double X=Y bonds.
CHEMISTRY-A EUROPEAN JOURNAL
(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, 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
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
Joshua S. Sapsford, Daniel Csokas, Roland C. Turnell-Ritson, Liam A. Parkin, Andrew D. Crawford, Imre Papai, Andrew E. Ashley
Summary: The newly synthesized compound iPr(3)SnNTf(2) exhibits stronger Lewis acid properties compared to previously studied compounds, enabling faster hydrogen activation and catalytic hydrolysis of ester bonds. The reaction outcome is influenced by the steric and electronic properties of the substrate, with computational studies revealing differences in the reaction mechanisms between different ester substrates.
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
Angela Milinkovic, Antoine Dupe, Ferdinand Belaj, Nadia C. Moesch-Zanetti
Summary: Molybdenum(VI) bis(imido) complexes with frustrated Lewis pair characteristics can heterolytically split H-H, Si-H, and O-H bonds. These complexes can be used as catalysts for the hydrosilylation reaction. Mechanistic elucidation revealed the insertion of aldehydes into the B-H bond of the molybdenum complexes, highlighting the weakly coordinating cation behavior of molybdenum.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Review
Biochemistry & Molecular Biology
Suresh Mummadi, Clemens Krempner
Summary: The development and application of new organoboron reagents as Lewis acids have expanded over the past 20 years. This review focuses on the recent uses of BPh3 as a metal-free catalyst in various organic transformations. The catalytic applications include polymer synthesis, hydrogen cleavage, hydrogenation, N-methylation, C-methylation, cycloaddition, and insertion reactions. This mini-review highlights the underexplored potential of commercially available BPh3 in metal-free catalysis.
Article
Chemistry, Organic
Geeta Devi Yadav, Pooja Chaudhary, Balaram Pani, Surendra Singh
Summary: Chiral transition metal complexes with privileged ligands are efficient catalysts for various asymmetric organic transformations. Transition metal complexes of C1-symmetric pyrrolidine-based ligands have been widely used in asymmetric organic reactions. However, a comprehensive review article on the transition metal complexes of chiral C1-symmetric pyrrolidine-based ligands derived from (L)-proline has not been published.
TETRAHEDRON LETTERS
(2024)