ABSTRACT Frustrated Lewis pairs (FLPs) have attracted extensive attention in heterogeneous catalysis due to their distinctive ability to efficiently dissociate small molecules and accelerate reaction kinetics, yet challenges remain for low‐cost large‐scale applications. Herein, FLPs are first successfully fabricated in low‐cost silicate minerals, with the inherent surface hydroxyl groups (‐OH) of the latter serving as Lewis base (LB) sites. Simultaneously, H 2 ‐mediated deoxygenation induces oxygen vacancies (O V ), modulating the electronic states of adjacent Zn sites and transforms them into Lewis acid (LA) sites. Density functional theory (DFT) calculations are carried out to elucidate the optimal spatial distance between LA and LB sites and the charge transfer behavior, thereby furnishing atomic‐scale insights into the effective construction of FLPs. Coupled with in‐situ H 2 characterizations, the efficient dissociation of H 2 into H + and H − is directly visualized, thus affording abundant active hydrogen species for the subsequent reaction. Furthermore, FLPs can serve as shallow energy levels to facilitate the separation and migration of photogenerated carriers. The CO formation rate in photocatalytic reaction of the Zn 2 SiO 4 catalyst modified with FLPs is 2.3‐fold higher than that of the pristine FLPs‐free Zn 2 SiO 4 catalyst. This work provides a strategy for FLPs in low‐cost silicate minerals facilitating photocatalytic CO 2 hydrogenation.

Construction of surface frustrated Lewis pairs on Co–doped N–carbon nanosheets for highly efficient activation of peroxymonosulfate toward rapid organic pollutant degradation

Metal-Free Solid Frustrated Lewis Pair Catalyst for Phenylacetylene Semihydrogenation

Construction of stable and highly crystalline chiral frustrated Lewis pair (FLP) frameworks can enhance their prospects for application in practical transformation reactions; however, the scarcity of synthetic approaches has strongly hindered the development of chiral FLP frameworks. Based on the conformational chirality theory, we successfully prepared a series of chiral Lewis base-centered covalent organic frameworks (PCOFs) by leveraging the chiral memory effect during the dynamic cage-to-COF transformation. Subsequent integration of these PCOFs with tris(pentafluorophenyl)borane afforded chiral FLP frameworks (CFLPs), which efficiently catalyzed the asymmetric hydrogenation of imines. CFLP-1 exhibited optimal catalytic performance, facilitating the hydrosilylation of imines with a product yield exceeding 99% and an enantiomeric excess (ee) of 85%. CFLP-1 was then deposited onto a nylon membrane to fabricate a CFLP-nylon composite membrane. This modification not only significantly enhanced the reaction rate but also enabled chiral resolution of the product, achieving a turnover frequency (TOF) of 209.37 h- 1 and an ee value of 98%. These results demonstrate that the novel CFLP material has broad application prospects in heterogeneous asymmetric catalysis and enantiomeric separation.

Abstract Coordination of a Lewis base to a tricoordinate boryl group generates a tetracoordinate species, thereby inverting the electronic character of the boryl substituents from electron‐accepting to electron‐donating. Utilizing this π‐umpolung strategy, we report temperature‐responsive fluorophores that emit in the near‐infrared (NIR) region. To achieve reversible π‐umpolung, we designed a diarylboryl unit in which two aryl rings are tethered by an alkenyl linker. This alkenyl‐strapped scaffold engages in a weak olefin–borane interaction and undergoes frustrated Lewis pair (FLP)‐type addition even with bulky neutral Lewis bases such as tricyclohexylphosphine (PCy 3 ). When boryl groups are installed at both termini of 4,7‐di(2‐thienyl)‐2,1,3‐benzothiadiazole, coordination of PCy 3 induces pronounced red‐shifts in the emission spectra. In polar acetonitrile, the emission maximum reaches 732 nm, entering the NIR region. This red shift arises from the strong σ‐donating character of the resulting tetracoordinate boron centers, which enhance intramolecular charge transfer (ICT) character in the excited state. Unlike conventional dimesitylborane–fluoride complexes, the FLP‐type adducts exhibit reversible, temperature‐dependent shifts in the dissociation/association equilibrium. Although the solvent polarity influences the equilibrium, modulation of phosphine Lewis basicity enables reversible dissociation even in polar media, allowing this system to display large emission changes spanning the visible to NIR region.

The alkaline hydrogen evolution reaction (HER) associated with anion exchange membrane water electrolyzers (AEMWEs) is kinetically hindered by sluggish water dissociation and complex intermediate adsorption, which previous reports have inadequately addressed through isolated optimization, neglecting the intrinsic coupling between HER elementary steps. Herein, we report a frustrated Lewis pairs (FLPs) catalyst comprising NiRu dual single-atoms and adjacent NiRu nanoclusters anchored on nitrogen-doped carbon (Ni1Ru1-NiRu@NC), mimicking the enzymatic positive feedback mechanism that drives a self-reinforcing catalytic cycle and accelerates the coupled elementary steps in a cascade manner. The catalyst featuring spatially proximate Lewis acid and base sites enable sequential reaction steps, where water dissociation occurs at acid sites and hydrogen adsorption proceed at base sites. The two steps are bridged through rapid hydrogen spillover channel, constructing a closed catalytic circuit in which hydrogen consumption at base sites promotes continuous water dissociation at acid sites. Benefiting from this positive feedback loop, Ni1Ru1-NiRu@NC achieves a remarkable HER performance and exhibits exceptional long-term durability (>1000h at 1.0 A cm- 2) in AEMWEs. Our findings demonstrate a new strategy to integrate positive feedback-driven, cascade-coupled catalysis in FLPs systems, offering a promising pathway toward high-performance alkaline HER catalysts for industrial application.

The direct photooxidation of methane to value-added products presents a promising solution for the utilization of abundant natural gas resources. However, there are still great challenges in the production of multiple oxidation products and inevitable overoxidation owing to the difficult manipulation of C-H bond activation and alternative radical formation. Herein, the high-density In(L)-Ov-In-OH frustrated Lewis pairs (FLPs) with Lewis acidic In(L) and Lewis basic In-OH were constructed on the Pt-mIn2O3-x(OH)y photocatalyst to promote the C-H bond activation in CH4. In situ characterization techniques and theoretical calculations revealed that the electron transfer from the bonding orbitals (σ) of CH4 to the unoccupied orbitals of In(L), coupled with the weak electron donation from the In-OH sites to the antibonding orbitals (σ*) of CH4, cooperatively polarized and stretched the C-H bond, thus significantly lowering its dissociation energy barrier. Meanwhile, the tailored Pt-O-In motifs (either Pt nanoparticles or Pt single atoms) on the Pt-mIn2O3-x(OH)y photocatalyst serving as an electron acceptor could precisely modulate the types of reactive oxygen species by altering the adsorption configuration of O2. Benefiting from the synergy of the In(L)-Ov-In-OH FLPs and Pt motifs, both excellent yield and selectivity were obtained for CH3OH or HCHO. Under optimal conditions, Pt nanoparticles supported on mIn2O3-x(OH)y (PtNPs-mIn2O3-x(OH)y) achieved a high CH3OH production rate of 3970.0 μmol g-1 h-1 with 90.9% selectivity, and Pt single atoms coordinated with mIn2O3-x(OH)y (PtSAs-mIn2O3-x(OH)y) delivered an excellent HCHO yield of 10182.4 μmol g-1 h-1 with 84.9% selectivity. This work demonstrated a promising strategy for designing advanced photocatalysts to disentangle the activity-selectivity trade-off in CH4 photooxidation.

The semi-hydrogenation of alkynols to enols represents a vital industrial reaction for fine chemical synthesis, yet developing highly selective non-noble metal catalysts remains an urgent challenge. Herein, we report a Co3O4 nanorod (Co3O4-NR) catalyst with abundant solid-frustrated Lewis pairs (SFLPs) on specifically exposed {110} facets, where coordinatively unsaturated Co2+ acts as Lewis acid site whilst the surface hydroxyl group serves as Lewis base site. The Co3O4-NR catalyst exhibits exceptional performance toward semi-hydrogenation from 3-butyn-1-ol to 3-buten-1-ol with a product yield of 88.2%, which is preponderate to other non-noble metal catalysts. Poisoning experiments, in situ DRIFTS and theoretical calculations verify that the SFLPs sites serve as intrinsic active centers for H2 activation/dissociation and substrate adsorption. The hydrogenation of key intermediate (C4H7O*) is identified as the rate-determining step, where Hδ+ species strongly tethered to surface-OH group suppresses over-hydrogenation and thereby enhances the semi-hydrogenation selectivity. Projected density of states (PDOS) analysis reveals an accelerated hydrogenation kinetics via d-p orbital hybridization between Co 3d orbitals and C 2p orbitals in C4H7O*. This work advances the design of efficient and cost-effective SFLPs-based heterogeneous catalysts, which shows potential application in the synthesis of fine chemicals.

Sulphur-bridged frustrated Lewis pairs (FLPs) of the type Bis2E-S-PtBu2 (ESP; E = Al, Ga) were synthesised in analogy to their oxygen-bridged E-O-P analogues (EOP). An exchange reaction between AlSP and GaOP affords selectively and in accordance with the concept of hard and soft acids and bases (HSAB) the inverted systems AlOP and GaSP. Reactivity studies towards small molecules, such as CO2, CS2, SO2, N2O, and propylene sulphide, revealed differences in adduct formations. The adducts EXP·CX2 and EXP·SO2 (X = O, S) consist of five-membered heterocylces. The oxidation products EXP·X are four-membered rings; they result from the reaction of the EXP with N2O and/or propylene sulfide (under loss of propene), except the reaction of AlSP with propylene sulfide that forms a six-membered ring with the whole substrate molecule. The FLP GaSP is exceptional because the formation of its CO2 adduct is temperature-dependent, confirmed by variable-temperature NMR studies, and its adduct GaSP·CS2 has two structural isomers. All CS2 adducts impress with different colours in solution.

Frustrated Lewis pairs (FLPs), composed of reactive combinations of Lewis acids (LAs) and bases (LBs) offer a metal-free platform for catalyzing a wide range of chemical transformations. Designing the optimal...

The photoelectrocatalytic water splitting was impeded by high thermodynamic energy barriers and slow reaction kinetics of anodic oxygen evolution reactions. Herein, a strategy for constructing frustrated Lewis pairs (FLPs) at...

Constructing frustrated Lewis pairs on defect-engineered biphasic catalysts for polyester depolymerization

Construction of frustrated Lewis pairs based on in-situ nitrogen-doped polymer-derived porous carbon for CO2 capture and conversion

Dual active sites of electron-rich Ni0 and frustrated Lewis pairs of Sr-doped catalysts for efficient fuel steam reforming

Structures and reactivities of heterogeneous frustrated Lewis pairs catalysts

Water reduction using p-block compounds has recently gained attention over traditional methods involving transition-metal complexes. Building on prior work on boron-phosphorus-based frustrated Lewis pairs (FLPs), specifically the bisborylphosphine (BPB) and borylphosphine (BP) systems, we here use density functional theory (DFT) to model water splitting, in which the nucleophilic substitution step plays a key role. Understanding this step computationally is crucial for deriving design rules for water splitting. However, the complete mechanistic details and the influence of substituents on the computed nucleophilic-substitution energy barrier remain unclear. In this theoretical study, we calculate reaction profiles for BPB and BP while systematically varying the substituents on borane (R1) and phosphorus (R2) to modulate steric and electron-withdrawing/donating properties. Our results indicate that BPB exhibits lower barriers than BP. According to the distortion-interaction analysis, when the borane receptor B2 is intermolecular (BP) it undergoes greater geometric distortion upon hydride transfer than in BPB, where the borane receptor is intramolecular. Despite the high computed barriers for BP, these can be reduced (rendering BP competitive with BPB) by incorporating strongly electron-donating R2 substituents at the phosphorus.

ABSTRACT Efficient catalysis of unsaturated hydrocarbon hydrogenation/isomerization reactions is important for realizing sustainable chemical processes and enhancing the whole energy efficiency. However, the development of “one‐pot” catalysts with high activity, excellent selectivity and outstanding stability remains a major challenge. This study presents a novel catalyst design that utilizes NU‐1000 with open metal sites to enhance metal‐molecule interactions and promote selective adsorption. By using a strategic multimetal doping technique Ti/Zr/Hf, homomeric high‐density frustrated Lewis pairs (FLPs) architecture with different coordination metals namely M‐NU‐1000‐X (M=Zr, Hf, Ti, X = 1~6 represented various metal combinations) were obtained. The strategic multimetal doping finely tune FLPs’ acidity/basicity and electron structure favorable for improve acid‐base synergism effect and steric hindrance effect. DFT calculations reveal a mechanism that generated active hydrogen through cleaving H 2 at the FLPs site then attack cycloolefin double bond selectively. The hydrogenation/isomerization mechanism was promoted greatly by catalysis effect induced by metals‐based π anti‐donation effect. Furthermore, we constructed a robust connection model between the calculated Gibbs free energy values of the transition state and some parameter and obtained activation energy barriers based on the descriptor model, thus significantly decreasing huge computational cost. Dynamic Time Warping (DTW) analysis reveals that the dynamic response of polarizability and LUMO energy levels is a key factor determining catalytic activity. The introduction of Ti significantly enhances these dynamic differences, while dynamic site regulation of the local coordination environment further amplifies the differentiation in catalytic performance. A novel approach has been established that integrates electronic structure properties, reaction path evolution, and energy descriptors. This opens a new gateway for developing highly efficient hydrogenation catalysts and provides innovative strategies for catalyst design.

Abstract The electrophilic C–H borylation of unactivated and deactivated, electron-poor arenes is a challenging reaction even with the most electrophilic borenium-ion species. We now report the transition-metal-free borylation of a wide range of aromatics and polyaromatics with a pyramidal boron Lewis superacid from the 9-boratriptycene family. The mechanism of formation of a highly reactive pyramidal boron Lewis superacid and the origin of the slow and continuous release of this highly reactive borylation reagent in the presence of a Lewis base are reminiscent of the reactions of latent frustrated Lewis pairs with small molecules.

Flash Communication: Clarifying the Synthesis of 4,5-Dibromo-9,9-dimethyl-9 <i>H</i> -xanthene: A Scaffold for Organometallic Ligands and Frustrated Lewis Pairs

Frustrated Lewis pairs (FLPs) have emerged as versatile metal-free catalysts for small-molecule activation, and strategies to control frustration through geometric immobilization and electronic tuning remain a topic of significant interest. Carborane cages, with their unique coordination-dependent electronic effects, have recently been shown to modulate FLP frustration. In this work, we introduce o-silaborane cages, whose coordination-based electronic effects had not previously been explored for modulating FLP reactivity. The -BH2 and -PH2 substituents were strategically placed at distinct coordinating sites of the cages to systematically compare the coordination dichotomy of o-carborane and o-silaborane frameworks in influencing the frustration of Lewis pairs. CO2 activation was employed as the model reaction to assess and compare these effects. Electronic structure analysis reveals that silaborane exerts stronger electron-withdrawing and electron-donating influences than carborane, leading to pronounced differences in acidity-basicity balance, strain distribution, and the stability of CO2 complexes. Furthermore, transition-state energetics demonstrate that site-dependent positioning of Lewis acid-base centres critically governs activation barriers. In the o-carborane framework, the acid and base groups positioned at the 1,4-sites exhibit the highest reactivity, whereas in the o-silaborane system, the 4,9-substituted arrangement is identified as the most reactive. These findings establish silaborane as a promising bridging unit, opening new design pathways for tuneable FLP-based CO2 utilization and broader small-molecule activation.