Lewis Acid Research Articles

Sterically Controlled Lewis Acid-Base Interaction Toward para-Selective Borylation of Aromatic Aldimines and Benzylamines.

Site-selective C-H bond functionalization of arenes at the para position remains extremely challenging primarily due to its relative inaccessibility from the catalytic site. As a consequence, it is significantly restricted to the limited molecular scaffolds. Herein, we report a method for the para-C-H borylation of aromatic aldimines and benzylamines using commercially available ligands under iridium catalysis. The established method displayed excellent para-selectivity for variously substituted aromatic aldimines, benzylamines and bioactive molecules. Based on the several control experiments, it has been realized that a Lewis acid-base interaction between the nitrogen and boron functionality guides the para selectivity via a steric shield for the aromatic aldimines, where Bpin acts as a transient directing group. However, the steric shield of the in situ generated N-Bpin moiety controlled the overall selectivity for the para borylation of benzylamines.

Defect Engineering in Ce-Based Metal-Organic Frameworks toward Enhanced Catalytic Performance for Hydrogenation of Dicyclopentadiene.

Defective metal-organic frameworks (MOFs) have shown great potential for catalysis due to abundant active sites and adjustable physical and chemical properties. A series of Ce-based MOFs with different defect contents were synthesized via a modulator-induced defect engineering strategy with the aid of the cell pulverization technique. The effects of modulators on the pore structure, morphology, valence distribution of Ce, and Lewis acidity of Ce-MOF-801 were systematically investigated. Among the different samples studied, the optimal Ce-MOF-801-50eq sample exhibited remarkable catalytic activity for DCPD hydrogenation, achieving a conversion rate of 100%, which is significantly higher compared to other Ce-MOF-801-neq samples as well as the Zr-MOF-801-50eq and Hf-MOF-801-50eq samples. The enhanced catalytic performance of Ce-MOF-801-50eq can be attributed to advantages provided by defect engineering, such as the high specific surface area, proper pore size distribution, abundant unsaturated metal sites, and Ce3+/Ce4+ atom ratio, which have been supported by various characterizations. This study provides important insights into the rational design of Ce-MOFs in the field of catalytic DCPD hydrogenation.

Engineered Electron-Deficient Sites at Boron-Doped Strontium Titanate/Electrolyte Interfaces Accelerate the Electrocatalytic Reduction of N2 to NH3: A Combined DFT and Experimental Electrocatalysis Study.

The development of an efficient, selective, and durable catalysis system for the electrocatalytic N2 reduction reaction (ENRR) is a promising strategy for the sustainable production of ammonia. The high-performance ENRR is limited by two major challenges: poor adsorption of N2 over the catalyst surface and abysmal N2 solubility in aqueous electrolytes. Herein, with the help of our combined density functional theory (DFT) calculations and experimental electrocatalysis study, we demonstrate that concurrently induced electron-deficient Lewis acid sites in an electrocatalyst and in an electrolyte medium can significantly boost the ENRR performance. The DFT calculations, ex situ X-ray photoelectron and FTIR spectroscopy, electrochemical measurements, and N2-TPD (temperature-programmed desorption) over boron-doped strontium titanate (BSTO) samples reveal that the Lewis acid-base interactions of N2 synergistically enhance the adsorption and activation of N2. Besides, the B-dopant induces the defect sites (oxygen vacancies and Ti3+) that assist in enhanced N2 adsorption and results in suppressed hydrogen evolution due to B-induced electron-deficient sites for H+ adsorption. The insights from the DFT study evince that B prefers the Srtop position (on top of Sr) where N2 adsorbs in an end-on configuration, which favors the associative alternating pathway and suppresses the competitive hydrogen evolution. Thus, our combined experimental and DFT study demonstrates an insight toward enhancing the ENRR performance along with the suppressed hydrogen evolution via concurrently engineered electron-deficient sites at electrode and electrolyte interfaces.

Ab Initio Investigation of Tetrel Bonds in Isolated Complexes Formed Between a Lewis Acid H3MX, M-O or M-S (M = Si, Ge, or Sn) and the Lewis Bases B = N2, CO, HCCH, PH3, C2H4, HCN, CS, HNC, NP, H2O, and NH3.

Isolated complexes of the type B⋯A in which the noncovalent interaction is a tetrel bond have been characterized by ab initio calculations at the CCSD(T)(F12c)/cc-pVDZ-F12 level. The Lewis bases B involved were N2, CO, HCCH, PH3, C2H4, HCN, CS, HNC, NP, H2O and NH3. Two types of Lewis acid A were examined, each containing one of the tetrel atoms M = Si, Ge or Sn, The Lewis acids in the first series were the H3MX (X = F, Cl, CN, H), in each of which the most electrophilic region was found to lie on the C3 axis of the C3v molecules, near to the tetrel atom M. In the second series the Lewis acids were M-O and M-S. Graphs, consisting of calculated equilibrium dissociation energies De of each B⋯H3MX complex plotted against the nucleophilicities NB of the Lewis bases B, were used to obtain the electrophilicity EH3MX of each molecule H3MX (M = Si, Ge, Sn). The molecular electrostatic surface of potentials of the molecules M-S and M-O (M = Si, Ge, Sn) revealed that many of the B⋯M-S and B⋯M-O complexes should have a tetrel bond to M in which the axis of the M-S or M-O subunit should be approximately perpendicular to the axis of the nonbonding or π-bonding electron pair carried by B, a novel type of tetrel bond confirmed by geometry optimizations of the complexes.

Luminescent Platinum(II) Complexes with Stimuli-Responsive Flexible Lewis Pair Ligands: Spectroscopic and Computational Studies.

A series of new luminescent bimetallic platinum(II) complexes with stimuli-responsive flexible Lewis pair (FlexLP) ligands are described. The FlexLP ligands consist of a dimesitylboron Lewis acid and diphenylphosphine oxide Lewis base which are in equilibrium between the unbound open form and the Lewis adduct, controlled by the hydrogen bond donating strength of the solvent. Spectroscopic techniques and density functional theory (DFT) calculations were used to interpret the photophysics of the platinum(II) complexes. All complexes exhibit tunable absorption in the region of 300-500 nm and green to orange photoluminescence, depending on the ratio of weak (THF) to strong (MeOH) hydrogen bond donating solvent employed. Spectroscopic and computational data shows that phosphine and peripheral acetylide ligands on the platinum(II) centers have limited influence on the emission energy, indicating the emission originates from the FlexLP-dominated fluorescence. Using time-resolved transient absorption spectroscopy it is shown that the complexes undergo intersystem crossing (ISC) to the triplet-excited state upon photoexcitation, and the ISC efficiency is affected by the peripheral acetylide ligands. The triplet-excited state lifetime can also be manipulated by the state of the FlexLP ligand, with the closed form complexes having longer lifetimes than the open form complexes.

Visible Light-Induced Oxy-perfluoroalkylation of Olefins via Ternary Electron Donor-Acceptor Complexes.

Perfluoroalkyl iodides generally formed electron donor-acceptor (EDA) complexes by halogen bonding with a nitrogen atom containing Lewis bases. Since the electronegativity of the oxygen atom is stronger than that of the nitrogen atom, the resulting Rf-I···O-type halogen bonding EDA complex is less inclined to undergo electron transfer. Here, we reported rare ternary EDA complexes among perfluoroalkyl iodide, oxygen atom, and base. Mechanism experiments and density functional theory theoretical (DFT) calculations indicated that a base-promoted proton-coupled electron transfer (PCET) process was involved in this photochemical reaction. The intracomplex electron transfer event generated two radical species, perfluoroalkyl radical and TEMPO radical, enabling the subsequent oxy-perfluoroalkylation of olefins.

Insight into the Mechanism of CO2 Chemical Fixation into Epoxides by Windmill-Shaped Polyoxovanadate and n-Bu4NX (X = Br, I).

Carbon dioxide (CO2) coupled with epoxide to generate cyclic carbonate stands out in carbon neutrality due to its 100% atom utilization. In this work, the mechanism of CO2 cycloaddition with propylene oxide (PO) cocatalyzed by windmill-shaped polyoxovanadate, [(C2N2H8)4(CH3O)4VIV4VV4O16]·4CH3OH (V8-1), and n-Bu4NX (X = Br, I) was thoroughly investigated using density functional theory (DFT) calculations. The ring-opening, CO2-insertion, and ring-closing steps of the process were extensively studied. Our work emphasizes the synergistic effect between V8-1 and n-Bu4NX (X = Br, I). Through the analysis of an independent gradient model based on Hirshfeld partition (IGMH), it was found that the attack of n-Bu4NX (X = Br, I) on Cβ of PO triggers a distinct attractive interaction between the active fragment and the surrounding framework, serving as the primary driving force for the ring opening of PO. Furthermore, the effect of different cocatalysts was explored, with n-Bu4NI being more favorable than n-Bu4NBr. Moreover, the role of V8-1 in the CO2 cycloaddition reaction was clarified as not only acting as Lewis acid active sites but also serving as "electron sponges". This work is expected to advance the development of novel catalysts for organic carbonate formation.

Phosphine vs DBU-Catalyzed Annulation Reactions of β'-Acetoxy Allenoates with Acyl-Tethered Benzothiazole Bisnucleophiles: (4 + 3) or (4 + 1) vs (3 + 3) Annulation.

Dearomative annulation reaction of acyl-tethered benzothiazole bisnucleophiles with β'-acetoxy allenoates by switching the Lewis base is developed. The DBU-catalyzed reaction gives benzothiazole-fused 1,4-dihydropyridine carboxylates by (3 + 3) annulation chemoselectively. By contrast, the PR3-catalyzed reaction gives benzothiazole-fused azepines by (4 + 3) annulation and cyclopentene carboxylates by (4 + 1) annulation; the ratio of the latter two products depends on the solvent. A possible rationale for the difference in the reactivity, based on the 1,4/1,5-addition of the 2-acyl-tethered benzothiazole to the key phosphonium intermediate, is provided.

The First Main Group Element Lewis Acid Thionyl chloride Adduct and its Chemistry.

Although the adduct of aluminum trichloride with thionyl chloride has been reported, no thionyl chloride adduct of a main group element Lewis acid or organometallic compound has been structurally characterized. In this communication we present the synthesis and reactivity of the structurally ascertained adduct of thionyl chloride with tris(pentafluoroethyl)gallane as a representative of a main group element Lewis acid. Gallium and indium compounds with electron withdrawing groups, e.g. the pentafluoroethyl ligand, display versatile properties. While gallates and indates, [MR4]-, behave as weakly coordinating anions, neutral gallanes and indanes, MR3, are strong Lewis acids. Salts with the tetrakis(pentafluoroethyl)gallate and -indate, [M(C2F5)4]- (M=Ga, In), have recently been studied in detail. In contrast to this, work on the syntheses of the free Lewis superacids M(C2F5)3 (M= Ga, In) is scarce and underdeveloped. The hydrates [M(C2F5)3(OH2)2] proved to be suitable starting materials, particularly due to their thermal stability. Herein we report on synthesis and characterization of reactive adducts, [M(C2F5)3D], with the weak donor molecules (D) SOCl2 and Me3SiF. The effective Lewis acidities of Ga(C2F5)3 and In(C2F5)3 were experimentally deter-mined by the (modified) Gutmann-Beckett method and their catalytic potential is showcased.

The First Main Group Element Lewis Acid Thionyl chloride Adduct and its Chemistry

Although the adduct of aluminum trichloride with thionyl chloride has been reported, no thionyl chloride adduct of a main group element Lewis acid or organometallic compound has been structurally characterized. In this communication we present the synthesis and reactivity of the structurally ascertained adduct of thionyl chloride with tris(pentafluoroethyl)gallane as a representative of a main group element Lewis acid. Gallium and indium compounds with electron withdrawing groups, e.g. the pentafluoroethyl ligand, display versatile properties. While gallates and indates, [MR4]–, behave as weakly coordinating anions, neutral gallanes and indanes, MR3, are strong Lewis acids. Salts with the tetrakis(pentafluoroethyl)gallate and ‐indate, [M(C2F5)4]– (M=Ga, In), have recently been studied in detail. In contrast to this, work on the syntheses of the free Lewis superacids M(C2F5)3 (M= Ga, In) is scarce and underdeveloped. The hydrates [M(C2F5)3(OH2)2] proved to be suitable starting materials, particularly due to their thermal stability. Herein we report on synthesis and characterization of reactive adducts, [M(C2F5)3D], with the weak donor molecules (D) SOCl2 and Me3SiF. The effective Lewis acidities of Ga(C2F5)3 and In(C2F5)3 were experimentally deter­mined by the (modified) Gutmann‐Beckett method and their catalytic potential is showcased.

CO2‐mediated oxidative dehydrogenation of propane over Zn modified SSZ‐39 catalysts

To reveal the catalytic function of Brønsted acid sites (BAS) and different Zn Lewis acid sites (LAS) over SSZ‐39 and Zn modified SSZ‐39 in the direct dehydrogenation of propane (DHP) and CO­2‐mediated oxidative dehydrogenation (CO2‐ODHP) to propylene, a series of Zn‐modified H(Na)SSZ‐39 catalysts with various Zn loadings was prepared and conducted comparative studies between DHP and CO2‐ODHP. Detailed characterization results reveal the Zn‐loading‐dependent formation of Zn sites, primarily including Zn2+ and [Zn‐O‐Zn]2+, as well as their contributions in generating Lewis acid sites while neutralizing Brønsted acid sites of HSSZ‐39, namely bridged Si(OH)Al groups. In DHP, in comparison to bare HSSZ‐39, Zn/HSSZ‐39 catalysts exhibited a significantly enhanced C3H8 conversion. The presence of CO2 even further promoted C3H8 conversion in comparison to DHP. Given the above observations, we prepared Zn/NaSSZ‐39, in which the incorporation of Na further enriches the Lewis acid sites while neutralizing Brønsted acid sites of zeolite. Zn/NaSSZ‐39 even outperforms Zn/HSSZ‐39 catalysts with almost doubled C3H6 yield for CO2‐ODHP. The BAS has a poor CO2‐ODHP performance but can enhance the CO2 conversion towards CO significantly, while the Zn LAS is favorable for the CO2‐ODHP reaction, and plausible reaction paths of CO2‐ODHP on active sites are proposed.

Complexes of Zinc-Coordinated Heteroaromatic N-Oxides with Pyrene: Lewis Acid Effects on the Multicenter Donor–Acceptor Bonding

4-Nitroquinoline-N-oxide (NQO) and 4-nitropyridine-N-oxide (NPO) are important precursors for the synthesis of substituted heterocycles while NQO is a popular model mutagen and carcinogen broadly used in cancer research; intermolecular interactions are critical for their reactions or functioning in vivo. Herein, the effects of the coordination of N-oxide’s oxygen atom to Lewis acids on multicenter donor–acceptor bonding were explored via a combination of experimental and computational studies of the complexes of NQO and NPO with a typical π-electron donor, pyrene. Coordination with ZnCl2 increased the positive electrostatic potentials on the surfaces of these π-acceptors and lowered the energy of their LUMO. Analogous effects were observed upon the protonation of the N-oxides’ oxygen or bonding with boron trifluoride. The interaction of ZnCl2, NPO, or NQO and pyrene resulted in the formation of dark co-crystals comprising π-stacked Zn-coordinated N-oxides and pyrene similar to that found with protonated or (reported earlier) BF3-bonded N-oxides. Computational studies indicated that the coordination of N-oxides to zinc(II), BF3, or protonation led to the strengthening of the multicenter bonding of the nitro-heterocycle with pyrene, and this effect was related both to the increased electrostatic attraction and molecular–orbital interactions in their complexes.

From Building Blocks to Catalysts: The Underinvestigated Potential of Boronic Acid Esters.

Lewis acids are crucial in chemistry, with applications in pharmaceuticals, agrochemicals, and materials science. In main-group chemistry, they offer alternatives to transition metals, prompting our study of halogenated boronic acid esters (BAEs). Although BAEs are well-known, their catalytic potential has been overlooked. Our investigation found their Lewis acidity superior to that of boron trifluoride and comparable to that of tris(pentafluorophenyl)borane. Additionally, their catalysis of the Sakurai allylation of aldehydes has been documented, paving the way for future advancements.

Electric-controlled adsorption and surface energy of cyclodextrins

By applying the electro-capillary rise method to control the solvent adsorption behavior for α-, β-, and γ–cyclodextrin, CD, respectively, this work showed that the voltage increase can enhance the adsorption of polar solvents, e.g. the water and formamide, while keep the adsorption of non-polar solvents, e.g. the hexane and diiodomethane, stabilization for these CDs. In terms of recorded dynamic adsorption curves, the electric-controlled surface properties of those CDs were furthermore estimated. Results showed that the increase of both the number of glucose units and voltage can enhance the surface free energy of CD due to the Lewis acid-base property of CD increased accordingly. The Lifshitz-van der Waals component has been found the main component of the surface energy of CD and was greater with the smaller number of glucose units uninfluenced by the electricity variety.

Engineering Lewis-Acid Defects on ZnO Quantum Dots by Trace Transition-Metal Single Atoms for High Glycerol-to-Glycerol Carbonate Conversion.

Efficient conversion of biomass wastes into valuable chemicals has been regarded as a sustainable approach for green and circular economy. Herein, a highly efficient catalytic conversion of glycerol (Gly) into glycerol carbonate (GlyC) by carbonylation with the commercially available urea is presented using low-cost transition metal single atoms supported on zinc oxide quantum dots (M1-ZnO QDs) as a catalyst without using any solvent. A facile one-step wet chemical synthesis allows various types of metal single atoms to simultaneously dope and introduce Lewis-acid defects in the ZnO QD structure. It is found that doping with a trace amount of isolated metal atoms greatly boosts the catalytic activity with Gly conversion of 90.7%, GlyC selectivity of 100.0%, and GlyC yield of 90.6%. Congruential results from both Density Functional Theory (DFT)and in situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (in situ DRIFTS) studies reveal that the superior catalytic performance can be attributed to the enriched Lewis acid sites that endow optimal adsorption, formation of the intermediate for coupling between urea and Gly, and desorption of GlyC. Moreover, the tiny size of ZnO QDs efficiently promotes the accessibility of these active sites to the reactants.

23.81%-Efficiency Flexible Inverted Perovskite Solar Cells with Enhanced Stability and Flexibility via a Lewis Base Passivation.

Lewis base molecules bind the undercoordinated lead atoms at interfaces and grain boundaries, leading to the high efficiency and stability of flexible perovskite solar cells (PSCs). We demonstrated a highly efficient, stable, and flexible PSC via interface passivation using a Lewis base of tri(o-tolyl)phosphine (TTP). It not only induced an intimate interface contact and a complete deposition of the perovskite thin layers on hole transport layers (HTLs) but also led to a better perovskite with a raised crystallinity, fewer defects, and a better morphology, including fewer gullies, high uniformity, and low roughness. Furthermore, the TTP treatments induced a good alignment of energy levels among the perovskites, HTLs, and C60. The resultant flexible inverted PSCs exhibited a high power conversion efficiency (PCE) of 23.81%, which is one of the highest PCEs among these flexible inverted PSCs. Moreover, the optimized flexible PSCs exhibited high storage stability, superior operation stability, and enhanced mechanical flexibility. This study presents an effective method to substantially raise the PCE, stability, and mechanical flexibility of the flexible inverted perovskite photovoltaics.

Non-metallic Lewis acid sites enhance the activation of peracetic acid by cobalt-iron spinel for micropollutant decontamination: The critical role of Lewis acid sites as electron shuttles

Spinel is a common activator for peroxides, e.g., peracetic acid (PAA), in wastewater treatment, but suffers from insufficient electron transfer capacity at the active site and thus the limited activation capacity. Lewis acids are recognized for their capacity to interact with electrons and activate active sites, playing a crucial role in enhancing oxidant adsorption, shortening catalytic reaction distances, and increasing reaction kinetics. Herein, tellurium (Te), a typical Lewis acid, was introduced into cobalt-iron spinel (TCF) as an electron shuttler to improve the electron transfer capacity and thus boost the PAA activation. Results show that the degradation rate of sulfamethoxazole (SMX) with PAA activated via TCF is 4.0 times higher compared with cobalt-iron spinel (CF). Electron spin resonance (ESR) analysis and quenching experiments indicated acetylperoxyl radicals (CH3C(O)OO·) as the dominant reactive species in SMX degradation. Electrochemical tests revealed that the introduction of Lewis acid improved the charge transfer ability and charge utilization efficiency of the catalysts, exhibiting less electronic resistance and superior redox properties. Density functional theory (DFT) calculation suggests that the introduction of Lewis acid optimizes the electron distribution of the catalyst, and reduces the crucial reaction energy barriers for PAA activation. Additionally, the distinctive structural environment of Lewis acid renders TCF to exhibit excellent stability and resistance to complicated matrices in PAA activation. This work provides valuable insights into the Lewis acid regulating bimetallic catalyst performance and understanding the intrinsic interaction mechanisms, thereby establishing a critical groundwork for addressing prevailing wastewater treatment.

Iron-sulphur protein catalysed [4+2] cycloadditions in natural product biosynthesis

To the best of our knowledge, enzymes that catalyse intramolecular Diels-Alder ([4+2] cycloaddition) reactions are frequently reported in natural product biosynthesis; however, no native enzymes utilising Lewis acid catalysis have been reported. Verticilactam is a representative member of polycyclic macrolactams, presumably produced by spontaneous cycloaddition. We report that the intramolecular [4+2] cycloadditions can be significantly accelerated by ferredoxins (Fds), a class of small iron-sulphur (Fe-S) proteins. Through iron atom substitution by Lewis acidic gallium (Ga) iron and computational calculations, we confirm that the ubiquitous Fe-S cluster efficiently functions as Lewis acid to accelerate the tandem [4+2] cycloaddition and Michael addition reactions by lowering free energy barriers. Our work highlights Nature’s ingenious strategy to generate complex molecule structures using the ubiquitous Fe-S protein. Furthermore, our study sheds light on the future design of Fd as a versatile Lewis acid catalyst for [4+2] cycloaddition reactions.

Iron-sulphur protein catalysed [4+2] cycloadditions in natural product biosynthesis

To the best of our knowledge, enzymes that catalyse intramolecular Diels-Alder ([4+2] cycloaddition) reactions are frequently reported in natural product biosynthesis; however, no native enzymes utilising Lewis acid catalysis have been reported. Verticilactam is a representative member of polycyclic macrolactams, presumably produced by spontaneous cycloaddition. We report that the intramolecular [4+2] cycloadditions can be significantly accelerated by ferredoxins (Fds), a class of small iron-sulphur (Fe-S) proteins. Through iron atom substitution by Lewis acidic gallium (Ga) iron and computational calculations, we confirm that the ubiquitous Fe-S cluster efficiently functions as Lewis acid to accelerate the tandem [4+2] cycloaddition and Michael addition reactions by lowering free energy barriers. Our work highlights Nature’s ingenious strategy to generate complex molecule structures using the ubiquitous Fe-S protein. Furthermore, our study sheds light on the future design of Fd as a versatile Lewis acid catalyst for [4+2] cycloaddition reactions.

Lewis Acid-Base Pairs: The Bonding Rule of Closed-Shell M···M' Interactions (M = HgII/PdII; M' = AgI/AuI).

Metallophilic interactions are the widespread interactions in multimetal clusters to orientate closed-shell metal self-assembly form linear, facet, or block clusters. The closed-shell metal cation does not have empty valence orbitals, but is able to attract each other. It is still a conundrum to understand the resource in balancing the strong Coulomb repulsion between two cations. Most traditional descriptions attribute the counterintuitive attractions to London dispersion, Pauli repulsions, and ambiguous orbital interactions. However, neither the dispersion nor the unsourced donor-acceptor interaction can be applied to explain the saturability and directionality in multimetal clusters, where the M···M' structure is the basic molecular unit. Here, we clarify the origination of the covalency in closed-shell metallophilic interactions based on the study of heterobimetallic compounds composed of d10-d8 species (AgI/AuI-PdII) and d10-d10 species (AgI/AuI-HgII) obtained from experiments. The inner d electrons not only participate in the metallophilic interactions but also show different Lewis acidity and basicity in the formation of M···M' structures. The present work not only provides us a novel covalent perspective to visualize the closed-shell M···M' interactions but also unveils the truth of metallophilic interactions.