Lewis Acid Research Articles

Nanoclay Mediated Two-Pronged Strategy for Infected-Wound Healing.

Photothermal therapy (PTT) is an efficient way to combat bacterial infections and circumvent multidrug resistance. However, balancing efficacious bacterial killing and minimizing damage to the surrounding normal tissues remain a great challenge. Herein, a highly cooperative Prussian blue/kaolinite (PB/Kaol) hybrid nanosystem is constructed for antibacterial therapy to accelerate the healing of infected wounds. After hybridization with Kaol, the prepared PB/Kaol forms interfacial Al-O-Fe bonds, a fast charge transfer channel from Kaol to PB, which contributes to the enhanced photothermal effect of PB/Kaol. Additionally, the hydroxyl and Lewis acid-base sites of the Kaol surface could promote the adhesion of PB/Kaol to bacteria, thereby ensuring that as much hyperthermia as possible is focused on the bacteria and minimizing damage to the surrounding healthy tissues. Furthermore, PB/Kaol inherits the anti-inflammatory and hemostasis functions of PB and Kaol, resulting in the rapid healing of infected wounds.

Chlorodefluorination Induced by Gallium-Based Lewis Acids.

The reaction of [Ga(C2F5)3(FSiMe3)] with chlorotrimethylsilane leads to the selective substitution of the α-fluorine atoms by chlorine atoms and thus to the formation of [Ga(CCl2CF3)3(FSiMe3)]. The corresponding chlorogallate ion, [Ga(CCl2CF3)3Cl]-, could be isolated and structurally characterized as its tetraphenylphosphonium salt. The catalytic potential of [Ga(CCl2CF3)3(FSiMe3)] was demonstrated via the chlorodefluorination of Me3SiCF3, 2,2-difluoropropane and [PPh4][Ga(C2F5)4].

Synthesis of alumina/ferric oxide nanofibers and application to catalysts for ethanol dehydration reaction by adding palladium oxide

AbstractAlumina/ferric oxide (Al₂O₃/Fe₂O₃) composite nanofibers were fabricated via electrospinning followed by heat treatment. Structural characterization revealed mesoporous morphology with high porosity and surface area and uniform dispersion of catalytically active Fe₂O₃ nanoparticles. Catalytic evaluation for ethanol dehydration demonstrated superior performance for nanofibers containing 5 wt% Fe₂O₃, attributed to their unique structural features. Further enhancement was achieved by incorporating palladium oxide (PdO), resulting in improved catalytic activity, particularly in ethylene productivity. Surface acid properties were altered with PdO addition, suggesting a role of Lewis acid sites in augmenting catalytic performance. The developed PdO/Al₂O₃/Fe₂O₃ nanofibers exhibit stable performance over multiple cycles, offering promising prospects for efficient ethanol dehydration catalysts.

Borenium Ion Equivalents Stabilized by BICAAC and Their Implementation as Catalysts in Hydrosilylation of Carbonyls.

Hydride abstraction from the borane adduct, (BICAAC)‧BH3 afforded the hydride bridged dinuclear borenium ion equivalent complexes 1 and 2 that have been characterized by various spectroscopic and spectrometric techniques followed by the assessment of Lewis acidity using the Gutmann-Beckett method. The single crystal X-ray structure of complex 2 revealed the presence of discrete ions in the solid state. The complex (BICAAC)‧BH2(OTf) (3), obtained from the reaction of (BICAAC)‧BH3 with MeOTf, forms the corresponding boronium cations [(BICAAC)‧BH2(L)]+(OTf)- on reaction with Lewis bases (L = pyridine (4) and DMAP (5)). Complexes 1 and 2 demonstrated notable catalytic activity in the hydrosilylation of a diverse array of carbonyls using 1.0 mol% catalyst loading (achieving the highest turnover frequency (TOFmax) of up to 1200 h-1 with benzaldehyde. A broad substrate scope has been presented for aldehydes and ketones decorated with various electron-donating and withdrawing substituents along with this the hydrosilylation of a few para-quinone methides has also been presented.

In Situ Generated 1‐Naphthylmethyl Radicals From Bis(1‐Naphthylmethyl)tin Dichlorides: Utilization For C‐C, C‐N, and C‐O Bond‐Forming Reactions

The in situ‐generated 1‐naphthylmethyl radicals from the thermolysis of bis(1‐naphthylmethyl)tin dichlorides combine with persistent organic radicals, 4‐hydroxy‐TEMPO or 4‐oxo‐TEMPO designs C−O bond forming products. Subsequently, the C‐N bond occurs when the 1‐naphthylmethyl radicals unite with nitric oxide (NO) under a nitrogen atmosphere.In contrast, the oxidation instead of the addition reaction predominantly happens in the 1‐naphthylmethyl radicals when nitrogen dioxide contains a high oxidation state nitrogen center, i.e., N(IV) used.The by‐product, dodecanuclear organotin cages, with twelve peripheral naphthyl units, could be isolated from the 4‐hydroxy‐TEMPO reaction. Besides, the synthesis of unsymmetrical diarylmethanes RArCH2 (R = 1‐naphthyl, 2,4,6‐Me3C6H2, 3‐ and 4‐MeC6H4, phenyl, 4‐ClC6H4; Ar = 4‐MeOC6H4, 3,4‐, 2,4‐ and 2,5‐Me2C6H3) in high yields and with good regioselectivity is reported. This new methodology involves the iodine‐mediated thermolysis of bis(arylmethyl)tin dichlorides (RCH2)2SnCl2 and an excess of an arene. This reaction involves homolytic cleavage of Sn–C bonds to give arylmethyl radicals that react with iodine in the presence of SnCl2 to give the corresponding cations, which undergo electrophilic attack on the arene. Functionalised diarylmethanes have wide applications in pharmaceutical, agrochemical, and materials sciences. Alternative synthetic approaches to this class of organic compounds that avoid using a transition‐metal catalyst or a strong Lewis acid are desirable.

Electronic Structure of Diatomic Nickel Sulfide.

The nature of the Ni-S bond is investigated due to its role in the absorption of atmospheric Lewis acid gases such as SO2 and SO3 onto Ni surfaces. The vibrational frequency and electronic structure of NiS were predicted using CCSD(T), CASSCF, and internally contracted multireference configuration interaction (icMRCI) + Q. 43 density functional theory (DFT) functionals were benchmarked. CASSCF predicted the ground state of NiS to be the 5Δ state arising from the 3d8(3F)4s2 (3F) and 3d9(2D)4s (3D) electronic configurations of Ni. When dynamical correlation effects are included at the icMRCI + Q level, the ground state of Ni-S is predicted to be 3Σ- consistent with the experiment. The vibrational frequency of Ni-S is calculated to be 519.1 cm-1 at the icMRCI + Q level, in reasonable agreement with the experimental value of 512.68 cm-1. CCSD(T) predicts the frequency of Ni-S to be 543.2 cm-1 when extrapolated to the complete basis set (CBS) limit. The Feller-Peterson-Dixon value based on the CCSD(T)/CBS extrapolation for the bond dissociation energy of NiS is 350.6 kJ/mol, within <4 kJ/mol of experiment. Of the 43 DFT functionals, BP86 and O3LYP predicted the vibrational frequency in closest agreement with the experiment. The applicability of DFT to such acid gas systems was further demonstrated by calculating the energy for displacement of NiO by SO to yield NiS and O2. This displacement energy was calculated to be within experimental error for ∼50% of the DFT functionals, but large differences were also predicted for some functionals.

A Rare Example of a Gallium-Based Lewis Superacid: Synthesis and Reactivity of Ga(OTeF5)3.

The Lewis superacid Ga(OTeF5)3 has been synthesized and characterized, revealing a monomeric structure in solution and a dimeric structure in the solid state. Isolated adducts of Ga(OTeF5)3 with strong and weak Lewis bases have been characterized spectroscopically as well as by single-crystal X-ray diffractometry. The Lewis acidity of this new species has been evaluated by means of different experimental and theoretical methods, which has allowed to classify it as one of only a few examples of a gallium-based Lewis superacid. The high Lewis acidity of Ga(OTeF5)3 was used to amplify the strength of the Brønsted acid HOTeF5, leading to the protonation of diethyl ether. Furthermore, Ga(OTeF5)3 was utilized to access the strong oxidizing system Ga(OTeF5)3/Xe(OTeF5)2 in SO2ClF, which was successfully employed in the synthesis of the dimethyl chloronium salt [Cl(CH3)2][Ga(OTeF5)4], a strong electrophilic methylation reagent.

Molybdenum Complex-Catalyzed N-Alkylation of Bulky Primary and Secondary Amines.

Aliphatic allylic amines are present in a large number of complex and pharmaceutically relevant molecules. The direct amination of allylic electrophiles serves as the most common method toward the preparation of these motifs. However, the use of feedstock reaction components (allyl alcohol and aliphatic amine) in these transformations remains a great challenge. Such a challenge primarily stems from the high Lewis basicity and large steric hindrance of aliphatic amines, in addition to the low reactivity of allylic alcohols. Herein, we report a general solution to these challenges. The developed protocol allows an efficient allylic amination of allyl alcohols with sterically bulky aliphatic amines in the presence of an inexpensive earth-abundant molybdenum complex. This simple and economic protocol also enables regioselective branched amination; the practicality of the reaction was shown in an efficient, scaled-up synthesis of several drugs.

Ceric Ammonium Nitrate Oxidation of a MnII Complex Generates a Bis(μ-oxo)dimanganese(IV,IV) Product via a MnIV-Oxo Intermediate.

The oxidation of manganese complexes using ceric ammonium nitrate (CAN) is often complicated by the fact that cerium(IV) can serve as both an oxidant and a Lewis acid. In this work, we explore the reaction of CAN with the MnII complex [MnII(OTf)(DMMN4py)](OTf) (DMMN4py = N,N-bis(4-methoxy-3,5-dimethyl-2-pyridylmethyl)-N-bis(2-pyridyl)methylamine). We chose this complex as multiple oxidation products, including oxomanganese(IV) and bis(μ-oxo)dimanganese(III,IV) complexes, have previously been reported. We envisioned that knowledge of the spectral properties of these intermediates would aid in understanding the potential complexities of CAN oxidation reactions. The oxidation of [MnII(OTf)(DMMN4py)](OTf) with 2.0 equiv CAN in 9:1 (v/v) MeCN:H2O at 25 °C transiently forms the MnIV-oxo complex, but this species is formed in low yields and is unstable. The MnIV-oxo complex evolves to a new intermediate that had not been previously observed. At lower temperatures, the formation of this new intermediate is preceded by formation of the previously reported bis(μ-oxo)dimanganese(III,IV) complex. EPR and X-ray absorption experiments for the new intermediate provide strong evidence for its formulation as [MnIVMnIV(μ-O)2(DMMN4py)2]4+. This work establishes dinuclear MnIVMnIV species as products that must be considered in CAN oxidation reactions of MnII complexes and shows that both mononuclear MnIV-oxo and dinuclear MnIIIMnIV complexes can be intermediates in such reactions.

Cleavage of the Robust Silicon–Fluorine σ‐Bond Allows Silicon–Carbon Bond Formation: Synthetic Strategies Toward Ortho‐Silyl Aryl Phosphonates

AbstractA straightforward, mild, and transition‐metal‐free three‐component coupling reaction involving arynes, phosphites, and silyl fluorides was developed through Si−F bond activation. Although the Si−F bond is one of the strongest bonds, Si−C bond formation via Si−F bond cleavage with the assistance of bidentate silicon and phosphonium Lewis acids has been successfully achieved. This unprecedented strategy provides a facile approach for synthesizing ortho‐silyl‐substituted aryl phosphonates. Notably, this method allows the use of not only dialkylarylsilyl fluorides and diarylalkylsilyl fluorides but also triarylsilyl fluorides as coupling partners, which is uncommon in the field of arylsilane synthesis. Furthermore, a variety of ortho‐silyl‐substituted aryl phosphonates were produced in moderate to good yields with broad functional group tolerance. Additionally, the versatility of ortho‐silyl‐substituted aryl phosphonates was demonstrated by the elaboration of the products into a range of silicon‐containing compounds.

One-pot synthesis of copper phthalocyanine polymer: An efficient CO2 fixation catalyst

The chemical transformation of CO2 into high-value-added products is not only favourable to environmental preservation, but also promising for economy. Developing novel and practical catalysts play a critical role in facilitating conversion of CO2 and the synthesis of high value-added chemicals. Herein, we present the fabrication of biphenyl-typed copper phthalocyanine polymer (BPh-CuPc) from 4,4’-bis(3,4-dicyanophenoxy)biphenyl via a one-pot synthesis procedure, and application of it as a promising catalyst for CO2 conversion into cyclocarbonate. FTIR, XPS, UV–vis, TGA and SEM measurements confirm the successful fabrication of BPh-CuPc. Attributing to the existence of copper ions which can act as a Lewis acid to activate epoxide, and phthalocyanine rings that is positive for CO2 absorption, within the chemical framework of BPh-CuPc, it exhibits excellent catalytic activity for CO2 conversion into cyclic carbonates under mild conditions when combined with tetrabutylammonium iodide (TBAI). As a result, a 98 % yield and 99 % selectivity are obtained for the BPh-CuPc/TBAI system in CO2/propylene oxide conversion under condition of 90 °C, 8 h and 2.0 MPa. The obtained high yield and selectivity, as well as remarkable stability and versatility, validate the promising application of BPh-CuPc as a CO2 conversion catalyst. SynopsisAttributing to the existence of copper ions and phthalocyanine rings within the chemical framework, BPh-CuPc exhibits excellent catalytic activity for CO2 conversion into cyclic carbonates under mild conditions.

B-containing ionic liquid modified SBA-15 for CO2-epoxide coupling reaction metal-free catalysis

A novel external-skeleton B-containing ionic liquid modified SBA-15 catalyst BBN-Imi-SBA-15-I (BBN denotes borabicyclo[3.3.1]nonane, Imi represents imidazolium ionic liquid) was successfully constructed by a post-modification method for efficiently catalyzing CO2-epoxide coupling reaction under both metal- and solvent-free conditions. 5BBN-Imi-SBA-15-I (5 refers to the molar ratio of Si to B), thanks to its synergistic effects of Lewis acid, weak base sites from tertiary amine and quaternary ammonium, hydrogen bond group and nucleophilic group, displayed good catalytic activity with 97 % product yield and 99 % selectivity at 100 °C, 2 MPa in the absence of cocatalyst. The obtained catalyst demonstrated good recyclability during six consecutive catalytic runs, also presented generality for various mono-substitute epoxides. Through in-situ NH3 diffuse reflectance infrared Fourier transform spectroscopy (NH3-DRIFTS) characterization, the Lewis acidity of organo-boron was verified. Besides, kinetics research also proved the positive effect of multiple active components on efficient catalysis under milder conditions over SiO2-based metal-free catalysts.

Unveiling the influence of open metal sites in quasi ZIF-67 for eco-friendly catalysis of solvent-free aldehyde cyanosilylation

Quasi metal–organic frameworks (Q-MOFs) containing a high density of open metal centers are considered as an effective method of expanding the effectiveness of defective MOF-based catalysts. To achieve this, quasi ZIF-67 (Q-ZIF-67), having large scale structural defects in the framework, is produced through partial deligandation of ZIF-67 under controlled thermal treatment at 310 °C in air. This generates many unsaturated cobalt centers as Lewis acid sites, and results in the coexistence of micro and meso-pores within the Q-ZIF-67 network. Subsequently Q-ZIF-67 was employed in the catalytic cyanosilylation of benzaldehyde with trimethylsilyl cyanide, resulting in the corresponding cyanohydrin within 30 min under solvent free-conditions in air at 40 °C and room temperature with TOF values of 1.62, 1.53 min−1, respectively. The related cyanohydrin product was identified via 1H NMR. Importantly, Q-ZIF-67 displayed a highly efficient heterogeneous Lewis acid catalyst for the cyanosilylation of benzaldehyde compared to the pristine ZIF-67 and related cobalt oxide. Furthermore, investigating the impact of the electron-donating and electron-withdrawing para-substitutions on benzaldehyde revealed that electron-withdrawing groups are suitable for nucleophilic reactions. It was also observed that there was no significant decrease in catalytic activity after five catalytic runs. Thus, the Q-ZIF-67 has considerable potential as environmentally friendly catalyst for wide range of practical application in aldehyde cyanosilylation reactions.

Insights into the oxygen vacancies in titanium-aluminum composite oxides for Ru-catalyzed bio-oil upgrading using guaiacol as a model compound

The high quality liquid products obtained from upgrading of bio-oil through hydrogenation can serve as viable alternatives to fossil fuels, thereby alleviating the strain on energy supply. In this study, a series of titanium-aluminum composite oxides (TixAlyO) was prepared by a sol-gel method and used as supports to fabricate ruthenium (Ru)-based catalysts for the hydrogenolysis upgrading of bio-oil. Various techniques, including in situ pyridine adsorption-Fourier-transform infrared spectroscopy (in situ Py-FTIR), in situ CO diffuse-reflectance Fourier-transform infrared spectroscopy (in situ CO DRIFTS), and CO2 temperature-programmed desorption (CO2-TPD), were employed to characterize the physicochemical and electronic structures of the catalysts. Using guaiacol as a model compound for bio-oil, the compositions and structures of the TixAlyO supports, as well as the effect of calcination treatment of the supports in an N2 atmosphere, on the hydrogenolysis reactivity, were investigated in detail. The results indicated that the hydrogenolysis rate of Caromatic−O bonds showed a significant linear correlation with the oxygen vacancy/Lewis acid content. Furthermore, the presence of oxygen vacancies facilitated the formation of small Ru nanoparticles. Importantly, calcination of the support in an N2 atmosphere facilitated the formation of metal/oxide interface sites in the Ru/Ti5Al5O-N catalyst, further augmenting its Lewis acidity and reducing the activation energy for the hydrogenolysis of the Caromatic−O bonds. The hydrogenolysis rate of the Caromatic−O bond in guaiacol over the oxygen vacancy-rich catalyst Ru/Ti5Al5O-N was increased by a factor of 2–4 compared to those over Ru-based catalysts with a single oxide support. This study exemplified a novel strategy of oxygen vacancy-promoted hydrogenolysis upgrading of bio-oil.

Synthesis of prodelphinidin B2 3,3′′-digallate using AgOTf-mediated self-condensation

The Lewis acid mediated self-condensation of an epigallocatechin gallate derivative was examined. We found that AgOTf as a Lewis acid and diethylene glycol as a leaving group at C-4 position afforded a dimeric epigallocatechin gallate derivative in a moderate yield. The condensed product was applied to the synthesis of prodelphinidin B2 3,3′′-digallate.

Towards highly efficient and stable perovskite solar cells: suppressing ion migration by inorganic boric acid stabilizer

The poor stability of organic-inorganic perovskite solar cells is commonly ascribed to elevated ion migration, stemming from the low electronegativity of iodine. To address this issue, boric acid was chosen as a stabilizer for perovskite thin films. As a Lewis acid, the boric acid has a sp2 hybridized boron atom, which can readily accept a pair of electrons from iodine ion into their vacant unhybridized p orbital, and the formation of the Pb-O bond further increases the iodide migration barrier. The significantly increased barrier of the iodine ion migration was demonstrated by the improved phase stability of the perovskite film under an electric field and the obviously enhanced stability of the perovskite films under strong ultraviolet light. PSCs that included the BA stabilizer were able to achieve an enhanced PCE of 25.52%. The initial efficiency of BA-modified devices remained at 80% even after being aged for 1000hours at 85 ℃ under around 30% relative humidity (RH). When subjected to maximum power point tracking and 20-25% RH, the PCE of BA-modified devices maintained an initial efficiency of 80% after 1500hours.

Modification of Cs/SiO2 with Zr element through sol–gel method for production of methyl methacrylate via one-step aldol condensation

Development of effective cesium-based catalyst is important for methyl methacrylate (MMA) production via one-step aldol reaction. Herein, a kind of Cs/Zr-SiO2 catalyst was prepared by sol–gel method and the acid-base properties and their balance could be controllably regulated. The influence of catalyst preparation conditions including Si/Zr ratio and water content on the structure and acid-base properties of Cs/Zr-SiO2 was demonstrated, which consequentially affected catalytic performance. The formation of Si-O-Zr and Cs-O-Si structure was identified as the dominant Lewis acid and base sites and the acid site density can be enhanced by 1-fold when using sol–gel method. In addition, the MP conversion could reach 37 % with MMA selectivity of 85 % at the optimal condition. Kinetic studies revealed that the activation barrier on the modified 10Cs/Zr-SiO2 exhibited the lowest activation energy of 110.9 kJ/mol. Besides the initial catalytic activity could still maintain after 800 h recycling, with single-pass life of 160 h.

Deep level defect passivation for printable mesoporous CsSnI3 perovskite solar cells with efficiency above 10%

The lead-free inorganic perovskite CsSnI3 is considered as one of the best candidates for emerging photovoltaics. Nevertheless, CsSnI3-based perovskite solar cells experience a significant drop in performance due to the nonradiative recombination facilitated by trapping. Here, we show an electron donor passivation method to regulate deep-level defects for CsSnI3 perovskite with electron donor pyrrole. Experimental observations combined with theoretical simulations verify that the saturation of Tin dangling bonds with pyrrole on the CsSnI3 surface via a Lewis acid-base addition reaction can significantly reduce the density of deep-level defects. Consequently, the printable mesoporous perovskite solar cells with an FTO/compact-TiO2/mesoporous-TiO2/Al2O3/NiO/carbon framework device structure penetrated with CsSnI3 achieve a power conversion efficiency of up to 10.11%. To our knowledge, this represents the highest efficiency reported to date for lead-free perovskite-based printable mesoporous solar cells. Furthermore, the unencapsulated devices demonstrated remarkable long-term stability, retaining 92% of their initial efficiency even after 2400 h of aging in a nitrogen atmosphere.

A deep eutectic solvent with bifunctional acid sites treatment to upgrade a bamboo kraft pulp into a cellulose-acetate grade dissolving pulp

Valorization of non-wood pulp, such as bamboo bleached kraft pulp into high-purity cellulose acetate (CA)-grade dissolving pulp is crucial but challenging in China. Herein, a series of metal salt-based deep eutectic solvents (MSDESs) involving various ZnCl2-urea (U), ZnCl2-glycerol (G), and ZnCl2-lactic acid (LA) are comparatively investigated for this purpose. Thanks to the bifunctional acid sites of Lewis acid ZnCl2 and Brønsted acid LA, the ZnCl2-LA MSDES has the highest acidity (2.62) and interaction affinity to bamboo fibers, leading to the highest efficiency in simultaneous pulp purification and activation. As a result, the resultant upgraded pulp from ZnCl2-LA (DES3-F) features remarkable improvements in purity (from 80.8 % to 93.1 %), intrinsic viscosity (from 897 to 419 mg/L), and reactivity (from 18.1 % to 80.8 %). Moreover, the modified acetate product has a high degree of substitution of 2.84 and a yield of 75.5 %. In short, such a proposed MSDES treatment can offer a promising and alternative approach for the manufacture of high-quality dissolving pulp and its derivatives.

Modulating the chemical environment of Ni2+ for the oxidative dehydrogenation of ethane: The formation of LAS(Al3+/Ga3+)-Ni-OH site

The oxidative dehydrogenation of ethane to ethylene (ODHE) usually suffers from the issues of ethane conversion-ethylene selectivity seesaw. Herein, a series of alumina-supported Ni and Ga catalysts with different molar ratios of Ni to Ga were synthesized by facile impregnation method constructing the Lewis acid site (LAS) strategy to obtain great ethylene selectivity (97 %). The variation of Ni:Ga ratio adjusted the ionic substitution ability, redox ability and acidity, thus regulate the chemical environment of Ni2+ to the formation of LAS(Al3+/Ga3+)-Ni-OH structure, which was proposed to be the active site for selective oxidation of ethane to ethylene, as proved by H2-TPR, ToF-SIMS, quasi in-situ XPS and in-situ FTIR. Moreover, the probable mechanism of ODHE reaction was proposed that C2H6 molecules were mainly adsorbed on LAS sites and activated on Ni-OH site of the catalyst. The pulse test further suggested that O- was mainly associated with the generation of CO2 and Ni(2-n)+ was connected with the production of CH4. It is highlighted that adjusting the Ni-related species and oxygen species on the catalyst surface are crucial to further improve the ethylene selectivity.