B(C F ) and P(MeNCH CH ) N form a classical Lewis adduct, (C F ) BP(MeNCH CH ) N. Although (C F ) BP(MeNCH CH ) N does not exhibit spectroscopic evidence of dissociation into its constituent acid and base, products of frustrated Lewis pair (FLP) addition reactions are seen with PhNCO, PhCH N , PhNSO, and CO . Computational studies show that thermal access to the dissociated acid and base permits FLP reactivity to proceed. These results demonstrate that FLP reactivity extends across the entire continuum of equilibria governing Lewis acid-base adducts.
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http://dx.doi.org/10.1002/anie.201802385 | DOI Listing |
Chempluschem
January 2025
Keele University, School of Chemical & Physical Sciences, UNITED KINGDOM OF GREAT BRITAIN AND NORTHERN IRELAND.
Frustrated Lewis pairs (FLPs) have rapidly become one of the key metal-free catalysts for a variety of chemical transformations. Embedding these catalysts within a supramolecular assembly can offer improvements to factors such as recyclability and selectivity. In this review we discuss advances in this area, covering key supramolecular assemblies such as metal organic frameworks (MOFs), covalent organic frameworks (COFs), polymers and macrocycles.
View Article and Find Full Text PDFAcc Chem Res
January 2025
The Wolfson Catalysis Centre, Department of Chemistry, University of Oxford, Oxford OX1 3QR, U.K.
ConspectusThe discovery of reversible hydrogenation using metal-free phosphoborate species in 2006 marked the official advent of frustrated Lewis pair (FLP) chemistry. This breakthrough revolutionized homogeneous catalysis approaches and paved the way for innovative catalytic strategies. The unique reactivity of FLPs is attributed to the Lewis base (LB) and Lewis acid (LA) sites either in spatial separation or in equilibrium, which actively react with molecules.
View Article and Find Full Text PDFACS Appl Mater Interfaces
January 2025
State Key Laboratory of Molecular Engineering of Polymers, Fudan University, Shanghai 200433, China.
Frustrated Lewis pair chemistry (FLP) occupy a crucial position in nonmetal-mediated catalysis, especially toward activation of inert gas molecules. Yet, one formidable issue of homogeneous FLP catalysts is their instability on preservation and recycling. Here we contribute a general solution that marries the polyhedral oligomeric silsesquioxane (POSS) with a structurally specific frustrated Lewis acid to fabricate porous polymer networks, which can form water-insensitive heterogeneous FLP catalysts upon employing Lewis base substrates.
View Article and Find Full Text PDFJ Phys Chem A
January 2025
School of Applied Science and Humanities, Haldia Institute of Technology, ICARE Complex, Haldia 721657, India.
This study explores the reactivity of a new intermolecular P/B frustrated Lewis pair in the context of dinitrogen activation through a push-pull mechanism. The ab initio molecular dynamics model known as atom-centered density matrix propagation plays a pivotal role in elucidating the weakly associated encounter complex. In-depth analysis, mainly through intrinsic reaction coordinate calculations, supports a single-step mechanism.
View Article and Find Full Text PDFChemistry
January 2025
University of Oxford, Inorganic Chemistry Laboratory, UNITED KINGDOM OF GREAT BRITAIN AND NORTHERN IRELAND.
Combining experiment and theory, the mechanisms of H2 activation by the potassium-bridged aluminyl dimer K2[Al(NON)]2 (NON = 4,5-bis(2,6-diisopropylanilido)-2,7-di-tertbutyl-9,9-dimethylxanthene) and its monomeric K+-sequestered counterpart have been investigated. These systems show diverging reactivity towards the activation of dihydrogen, with the dimeric species undergoing formal oxidative addition of H2 at each Al centre under ambient conditions, and the monomer proving to be inert to dihydrogen addition. Noting that this K+ dependence is inconsistent with classical models of single-centre reactivity for carbene-like Al(I) species, we rationalize these observations instead by a cooperative frustrated Lewis pair (FLP)-type mechanism (for the dimer) in which the aluminium centre acts as the Lewis base and the K+ centres as Lewis acids.
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