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
Chemistry, Physical
Michael G. Guerzoni, Ayan Dasgupta, Emma Richards, Rebecca L. Melen
Summary: This article introduces a less-represented class of catalysts in the field of asymmetric catalysis - cooperative main-group Lewis acids and Lewis bases, and discusses their application in enantioselective transformations.
Article
Chemistry, Multidisciplinary
Chamila Manankandayalage, Daniel K. Unruh, Clemens Krempner
Summary: The intramolecular inverse frustrated Lewis pairs (FLPs) with weakly Lewis acidic boryl and strongly basic guanidino moieties were synthesized and characterized, demonstrating their capability to activate small molecules. These novel FLPs show promising potential in diverse chemical transformations.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Rakesh Parida, Ricardo Inostroza Rivera, Swapan Sinha, Santanab Giri
Summary: New frustrated Lewis pairs (FLPs) have been designed to improve the activation of molecular hydrogen, by modifying the ligands. Among the three new FLPs analyzed, [C2BNO(CN)(3)](3)B-P(Bu-t)(3) shows better performance in activating molecular hydrogen compared to the conventionally used FLP.
Article
Chemistry, Multidisciplinary
Jorge Juan Cabrera-Trujillo, Israel Fernandez
Summary: The presence of cyclopropenimine moiety in geminal frustrated Lewis pairs enhances the reactivity of the system towards small molecule activation by increasing the aromaticity strength of this fragment, leading to low energy barriers and high exergonic transformations.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Elena S. Osipova, Ekaterina S. Gulyaeva, Evgenii I. Gutsul, Vladislava A. Kirkina, Alexander A. Pavlov, Yulia V. Nelyubina, Andrea Rossin, Maurizio Peruzzini, Lina M. Epstein, Natalia V. Belkova, Oleg A. Filippov, Elena S. Shubina
Summary: The reaction between basic [(PCP)Pd(H)] and acidic [LWH(CO)(3)] leads to the formation of bimolecular complexes that catalyze dehydrogenation. Experimental and computational studies reveal the formation of a complex in the first step, where proton transfer is the rate-determining step.
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, Inorganic & Nuclear
Yanlin Pan, Jie Cui, Yongliang Wei, Zhaochao Xu, Tongdao Wang
Summary: Rare examples of B-H bond activation in a frustrated radical pair regime have been observed by treating TEMPO radicals with Piers' borane. The resulting zwitterionic products and geminal N/B frustrated Lewis pairs imply a one electron process. Our results provide insights into chemical bond activation via a single electron transfer.
DALTON TRANSACTIONS
(2021)
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, Inorganic & Nuclear
Orhi Esarte Palomero, Richard A. Jones
Summary: The synthesis of novel ferrocene tethered boramidinate frustrated Lewis pairs (FLPs) capable of sequentially capturing small molecules is reported. The reactivity of the boramidinate moieties can be tuned by altering the substituents and borane used in the reduction. Independent small molecule capture by each FLP has been demonstrated, allowing for sequential capture of different gaseous small molecules.
DALTON TRANSACTIONS
(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, Organic
Fuyu Xie, Jianghua He, Yuetao Zhang
Summary: This article presents a strategy for generating Frustrated radical pairs (FRP) using a Lewis acid and a Lewis base. The FRP can efficiently initiate atom-transfer radical addition (ATRA) reactions, resulting in high regioselectivity and high yields of fluoroalkylated compounds.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Lei Qin, Zhaoyin Zhang, Ruiqin Liu, Ming Zhou, Lili Zhao
Summary: DFT calculations were used to investigate the mechanism of S-S bond cleavage in disulfides by a frustrated Lewis pair. The calculations revealed that the reaction proceeds through the formation of a weak complex between the disulfide and the Lewis acid. The S-S bond can be activated by the Lewis base leading to its cleavage and the formation of the desired product. The mechanism was compared to that of H-H bond cleavages and it was found that a weak donor-acceptor complex is formed before S-S bond cleavage.
TETRAHEDRON LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Mohmmad Faizan, Ravinder Pawar
Summary: The increase in atmospheric CO2 has caused serious environmental problems, and capturing and utilizing CO2 as a carbon source for industrial chemicals production is an effective solution. In this study, Intramolecular Frustrated Lewis pairs (IFLPs) based on N-Heterocycles with boron group functionalization at the alpha-position to N were theoretically investigated. The results showed that the IFLPs can activate CO2 with minimal energy requirements, with an activation energy range of 8 to 14 kcal/mol.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2022)