Lewis Acid Research Articles

Multifunction magnetic chiral MOF composite: A novel post-synthetic super catalyst for enhancing the asymmetric CO2 fixation

Here in, a novel neutral Chiral Metal−Organic Framework (CMOF) composite, Cu(II)-l-proline/TCT/APTES/Fe3O4/MIL-101(Fe) (Cu(II)-HPro/TCT/APTES/Fe3O4/MIL-101(Fe)), has been derived from the chiral Cu(II)-l-proline complex (Cu(II)-HPro) attached to TCT/APTES/Fe3O4 and MIL-101(Fe). Achiral MIL-101(Fe) was chiralized by the incorporation of chiral Cu(II)-HPro complex anchored to TCT/APTES/Fe3O4 using ultrasonic-assisted electrostatic self-assembly technique (postsynthetic modification). The resulted super catalyst has chiral species acting as Lewis base sites, together with two active metal sites (Fe and Cu) acting as Lewis acid centers leading to multifunctionality. Due to chiral auxiliary Lewis bases and Lewis acids, the catalytic activity of the Cu(II)-HPro/TCT/APTES/Fe3O4/MIL-101(Fe) composite was evaluated in asymmetric catalysis of prochiral substrates. This asymmetric super catalyst has proved to be highly active in CO2 fixation reaction at ambient pressure, low-temperature, solvent-free medium with high conversion and enantioselectivity. Based on the results, enantiomeric excess (ee) [97 % (S)], carbonate selectivity (>99 %), and conversion (>99 %) all demonstrate the superior performance of the investigated catalytic system. Furthermore, the magnetic characteristic, together with excellent structure stability, leads to high recyclability for 7 runs without a significant reduction of catalytic activity. The outcomes showed that chiralization of MIL-101(Fe) could occur through a simple and green approach, which may be a practical way to create chiral multifunctionalized metal−organic frameworks (MOFs).

Interfacial hydrogen bond effect between CeO2 and g-C3N4 boosts conversion to adipic acid from aerobic oxidation of cyclohexane

The selective oxidation reaction of cyclohexane is one of the typical activated sp3 C-H reactions, and its product adipic acid (AA) is the indispensable raw material used to produce nylon. However, subjecting to the inertness of C-H bond and the great reactivity of AA, the targeted transformation of cyclohexane remains a challenge. Here, the interfacial hydrogen bond (IHD) was developed by anchoring CeO2 on graphite carbon nitride (g-C3N4) surface, which could boost targeted acquisition adipic acid from aerobic oxidation of cyclohexane. The results indicated that the IHD effect can be flexibly regulated by changing the ratio of Ce3+/Ce4+, further optimizing the properties of surface OH species and Lewis acid sites. Under the synergistic effect of Ce3+/Ce4+ and Lewis acid sites on reaction interface, the glorious performance (32.2% conversion of cyclohexane with 66.4% selectivity) was obtained over the as-prepared CeO2/g-C3N4 IHD system. In addition, the interfacial adsorption properties of cyclohexane were explored by the virtue of in situ infrared spectroscopy, revealing the IHD effect could tune the adsorption behavior of cyclohexanone and further improve the selectivity of AA. This work disclosed that engineering the interface hydrogen bond effect between CeO2 and g-C3N4 provided feasible strategies to obtain excellent catalyst for cyclohexane oxidation.

A Highly Sterically Encumbered Boron Lewis Acid Enabled by an Organotellurium-Based Ligand.

Lewis acidic boron compounds are ubiquitous in chemistry due to their numerous applications, yet tuning and optimizing their properties towards different purposes is still a challenging field of research. In this work, the boron-based Lewis acid B[OTeF3(C6F5)2]3 was synthesized by reaction of the teflate derivative HOTeF3(C6F5)2 with BCl3 or BCl3 ⋅ SMe2. This new compound presents a remarkably high thermal stability up to 300 °C, as well as one of the most sterically encumbered boron centres known in the literature. Theoretical and experimental methods revealed that B[OTeF3(C6F5)2]3 exhibits a comparable Lewis acidity to that of the well-known B(C6F5)3. The affinity of B[OTeF3(C6F5)2]3 towards pyridine was accessed by Isothermal Titration Calorimetry (ITC) and compared to that of B(OTeF5)3 and B(C6F5)3. The ligand-transfer reactivity of this new boron compound towards different fluorides was demonstrated by the formation of an anionic Au(III) complex and a hypervalent iodine(III) species.

Degradation of clofibric acid by ozonation assisted by Co-Ce-SBA-15: Role of interfacial electron migration

Restrained by the sluggish Ce redox cycle, Ce-SBA-15 exhibited the low electron transfer toward O3 activation. To this end, cobalt‑cerium co-doped SBA-15 with three-dimensional pore structure was designed using urea-assisted hydrothermal method and its activity was evaluated using Clofibric acid (CA) as target pollutant. XRD and N2 adsorption-desorption characterizations suggested that Co-Ce-SBA-15 possessed a three-dimensional pore structure with high order degree. py-FTIR, O2-TPD, H2-TPR, and in situ electrochemical characterizations indicated that compared with Ce-SBA-15 and Co-SBA-15, Co-Ce-SBA-15 had greater Lewis acid strength, electron transfer ability and oxygen reducibility. Co-Ce-SBA-15/O3 achieved the greater CA removal and mineralization rate, with 98.7 % CA removal and 58.3 % TOC removal were obtained in 90 min. Co-Ce-SBA-15/O3 process would be inhibited by the coexisting Cl−, NO3− and SO42−. Co-Ce-SBA-15 demonstrated the greater ozone utilization rate than those of monometallic SBA-15. Lewis acidic sites of Co and Ce were the main sites for activating O3. DFT results suggested that the obvious electron transfer existed among O3, Co and Ce Lewis acid sites. The conversion of Co3+/Co2+ and Ce4+/Ce3+ accelerated the interfacial electron transfer, which favored for conveying O3 into •OH. •OH was the primary reactive oxygen species involved in degrading CA. 8 kinds of intermediates were found during CA degradation and the possible degradation route was proposed. This study deepened the understanding of the cooperative effect of Co and Ce in catalytic ozonation process.

Complexation and disproportionation of group 4 metal (alkoxy) halides with phosphine oxides.

Group 4 Lewis acids are well-known catalysts and precursors for (non-aqueous) sol-gel chemistry. Titanium, zirconium and hafnium halides, and alkoxy halides are precursors for the controlled synthesis of nanocrystals, often in the presence of Lewis base. Here, we investigate the interaction of Lewis bases with the tetrahalides (MX4, X = Cl, Br) and metal alkoxy halides (MXx(OR)4-x, x = 1-3, R = OiPr, OtBu). The tetrahalides yield the expected Lewis acid-base adducts MX4L2 (L = tetrahydrofuran or phosphine oxide). The mixed alkoxy halides react with Lewis bases in a more complex way. 31P NMR spectroscopy reveals that excess of phosphine oxide yields predominantly the complexation product, while a (sub)stoichiometric amount of phosphine oxide causes disproportionation of the MXx(OR)4-x species into MXx+1(OR)3-x and MXx-1(OR)5-x. The combination of complexation and disproportionation yields an atypical Job plot. In the case of zirconium isopropoxy chlorides, we fitted the concentration of all observed species and extracted thermodynamic descriptors from the Job plot. The complexation equilibrium constant decreases in the series: ZrCl3(OiPr) > ZrCl2(OiPr)2 ≫ ZrCl(OiPr)3, while the disproportionation equilibrium constant follows the opposite trend. Using calculations at the DFT level of theory, we show that disproportionation is driven by the more energetically favorable Lewis acid-base complex formed with the more acidic species. We also gain more insight into the isomerism of the complexes. The disproportionation reaction turns out to be a general phenomenon, for titanium, zirconium and hafnium, for chlorides and bromides, and for isopropoxides and tert-butoxides.

Photogeneration of α-Bimetalloid Radicals via Selective Activation of Multifunctional C1 Units.

Light-driven strategies that enable the chemoselective activation of a specific bond in multifunctional systems are comparatively underexplored in comparison to transition-metal-based technologies, yet desirable when considering the controlled exploration of chemical space. With the current drive to discover next-generation therapeutics, reaction design that enables the strategic incorporation of an sp3 carbon center, containing multiple synthetic handles for the subsequent exploration of chemical space would be highly enabling. Here, we describe the photoactivation of ambiphilic C1 units to generate α-bimetalloid radicals using only a Lewis base and light source to directly activate the C-I bond. Interception of these transient radicals with various SOMOphiles enables the rapid synthesis of organic scaffolds containing synthetic handles (B, Si, and Ge) for subsequent orthogonal activation. In-depth theoretical and mechanistic studies reveal the prominent role of 2,6-lutidine in forming a photoactive charge transfer complex and in stabilizing in situ generated iodine radicals, as well as the influential role of the boron p-orbital in the activation/weakening of the C-I bond. This simple and efficient methodology enabled expedient access to functionalized 3D frameworks that can be further derivatized using available technologies for C-B and C-Si bond activation.

Boron-Nitrogen-Edged Biomass-Derived Carbon: A Multifunctional Approach for Colorimetric Detection of H2O2, Flame Retardancy, and Triboelectric Nanogenerator.

Enhancing the concentration and type of nitrogen (N) dopants within the Sp2-carbon domain of carbon recycled from biomass sources is an efficient approach to mimic CNT, GO, and rGO to activate oxidants such as H2O2, excluding toxic chemicals and limiting reaction steps. However, monitoring the kind and concentration of N species in the Sp2-C domain is unlikely with thermal treatments only. A high temperature for graphitization reduces N moieties, leading to low electron density. This inhibits H2O2 adsorption and activation on catalyst surfaces. In this study, coffee waste (CW) is converted into B, N-doped biochar (BXNbY) using boric acid-assisted pyrolysis (H3BO3mass = X and carbonization temperature = Y) under N2 to overcome the challenge. The B dopant regulates the concentration and type of N, provides Lewis's acid sites, and converts graphitic-N to pyridine-N in BXNbY. The optimized B3Nb900 exhibits excellent colorimetric sensing performance toward H2O2 with a low detection limit (36.9nM) and high selectivity in the presence of many interferences and milk samples due to high pyridinic-N and Sp2 domain sizes. Interestingly, B enhances other properties of N-containing CW-derived carbon and introduces self-extinguishing and tribopositive properties. Hence, BXNbY-coated polyurethane foam shows excellent flame retardancy and energy harvesting performance.

Two-Dimensional Cu(II)-MOF with Lewis Acid-Base Bifunctional Sites for Chemical Fixation of CO2 and Bioactive 1,4-DHP Synthesis via Hantzsch Condensation.

Five- and six-membered heterocycles containing nitrogen or oxygen have been considered as privileged scaffolds in organic chemistry and the chemical industry because of their usage in high-value commodities. Herein, we report a two-dimensional (2D) Cu(II)-based MOF catalyst, IITKGP-40, via the strategic employment of ample Lewis acid-base bifunctional sites (open metal nodes and free pyrazine moieties) along the pore wall. IITKGP-40 could convert toxic CO2 to cyclic carbonates in an atom-economical manner under solvent-free conditions and aromatic aldehyde to bioactive 1,4-DHPs via Hantzsch condensation. Exceptional catalytic performance (99%) and turnover number under mild reaction conditions for CO2 fixation using sterically hindered styrene oxide, and good-to-excellent yields for a wide range of aromatic aldehydes toward 1,4-dihydropyridines (1,4-DHPs) make IITKGP-40 promising as a multipurpose heterogeneous catalyst. Moreover, to demonstrate the practical utility of the catalyst, two biologically important drug molecules, diludine and nitrendipine analogue, have also been synthesized. IITKGP-40 is recyclable for at least three consecutive runs without significant loss of activity, making it promising for real-time applications.

Vinylidene rearrangements of internal borylalkynes via 1,2-boryl migration.

Vinylidene rearrangement of alkynes is a well-established and powerful method for alkyne transformations, while use of borylalkynes has remained largely unexplored. This paper describes vinylidene rearrangements of internal borylalkynes using a cationic ruthenium complex. This rearrangement is applicable to alkynes with both tri-(B(pin), B(dan)) and tetracoordinate (B(mida)) boryl groups, and the reaction rate is dramatically affected by the Lewis acidity of the boryl group. Mechanistic study revealed that the rearrangement proceeds via 1,2-boryl migration regardless of the coordination number of the boron center. The migration mode was elucidated by theoretical calculations to indicate that the migration of the tricoordinate boryl groups is an electrophilic process in contrast to the previous vinylidene rearrangements of internal alkynes with two carbon substituents.

Synthesis of Stable Cs-Rich FA-Cs Perovskite Solar Cells by Assistance of a Lewis Base Additive

Synthesis of Stable Cs-Rich FA-Cs Perovskite Solar Cells by Assistance of a Lewis Base Additive

Insights into the Distinct Behaviors between Bifunctional and Binary Organoborane Catalysts through Terpolymerization of Epoxide, CO2, and Anhydride

AbstractAlkyl borane compounds‐mediated polymerizations have expanded to Lewis pair polymerization, free radical polymerization, ionic ring‐opening polymerization, and polyhomologation. The bifunctional organoborane catalysts that contain the Lewis acid and ammonium or phosphonium salt in one molecule have demonstrated superior catalytic performance for ring‐opening polymerization of epoxides and ring‐opening copolymerization of epoxides and CO2 than their two‐component analogues, i.e., the blend of organoborane and ammonium or phosphonium salt. To explore the origin of the differences of the one‐component and two‐component organoborane catalysts, here we conducted a systematic investigation on the catalytic performances of these two kinds of organoborane catalysts via terpolymerization of epoxide, carbon dioxide and anhydride. The resultant terpolymers produced independently by bifunctional and binary organoborane catalyst exhibited distinct microstructures, where a series of gradient polyester‐polycarbonate terpolymers with varying polyester content were afforded using the bifunctional catalyst, while tapering diblock terpolymers were obtained using the binary system. The bifunctional catalyst enhances the competitiveness of CO2 insertion than anhydride, which leads to the premature incorporation of CO2 into the polymer chains and ultimately results in the formation of gradient terpolymers. DFT calculations revealed the role of electrostatic interaction and charge distribution caused by intramolecular synergistic effect for bifunctional organoborane catalyst.

Uncovering Factors Controlling Reactivity of Metal-TEMPO Reaction Systems in the Solid State and Solution.

Nitroxides find application in various areas of chemistry, and a more in-depth understanding of factors controlling their reactivity with metal complexes is warranted to promote further developments. Here, we report on the effect of the metal centre Lewis acidity on both the distribution of the O- and N-centered spin density in 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) and turning TEMPO from the O- to N-radical mode scavenger in metal-TEMPO systems. We use Et(Cl)Zn/TEMPO model reaction system with tuneable reactivity in the solid state and solution. Among various products, a unique Lewis acid-base adduct of Cl2Zn with the N-ethylated TEMPO was isolated and structurally characterised, and the so-called solid-state 'slow chemistry' reaction led to a higher yield of the N-alkylated product. The revealed structure-activity/selectivity correlations are exceptional yet are entirely rationalised by the mechanistic underpinning supported by theoretical calculations of studied model systems. This work lays a foundation and mechanistic blueprint for future metal/nitroxide systems exploration.

Modulating the Microstructure and Surface Acidity of MnO2 by Doping-Induced Phase Transition for Simultaneous Removal of Toluene and NOx at Low Temperature.

It is a great challenge to remove VOCs and NOx simultaneously from flue gas in nonelectric industries. This study focuses on the construction of Fe-MnO2 catalysts that perform well in the simultaneous removal of toluene and NOx at low temperatures. Utilizing the Fe-induced phase transition of MnO2, Fe-MnO2-F&R catalysts with a composite morphology of nanoflowers and nanorods were successfully prepared that provided an abundant microporous structure to facilitate the diffusion of molecules of different sizes. Through in-depth investigation of the active sites and reaction mechanism, we discovered that Fe-induced phase transition could modulate the surface acidity of Fe-MnO2-F&R. The higher concentration of surface Mn4+ provided numerous Brønsted acid sites, which effectively promoted the activation of toluene to reactive intermediates, such as benzyl alcohol/benzoate/maleic acid. Simultaneously, Fe provided a large number of Lewis acid sites that anchor and activate NH3 species, thereby inhibiting NH3 nonselective oxidation. Furthermore, additional Brønsted acid sites were generated during the simultaneous reaction process, enhancing toluene activation. Consequently, the simultaneous removal of toluene and NOx was achieved through regulation of the physical structure and the concentration of acidic sites. The present work provides new insights into the rational design of bifunctional catalysts for the synergistic control of VOCs and NOx emissions.

Convergent Paired Electrolysis for [3+2] Cycloaddition of Azidotrimethylsilane with N-Heterocycles.

A widely used method to obtain tetrazoles is through the azide and nitrile [3+2] cycloaddition. However, this process often involves using non-recyclable transition metals or Lewis acid catalysts and stoichiometric amounts of oxidants and additives, which reduces atom efficiency. We have discovered a convergent paired electrochemical reaction to perform this cycloaddition reaction, without the need for metal catalysts or oxidants. This tetrazolation strategy uses azidotrimethylsilane (TMSN3) and N-heterocycles in an undivided cell at a constant current. We use a mixture of CH3CN and equivalent amounts of H2O as co-solvent at room temperature. It is crucial to produce a stoichiometric amount of active hydroxyl ions through the cathodic reduction of water. Cyclic voltammetry (CV) studies and control experiments confirm that the cycloaddition reaction is specific to the electrode electron transfer process, eliminating the need for a mediator to shuttle electrons. This metal- and oxidant-free strategy is highly compatible with different functional groups and produces products with moderate to good yields. We have successfully tetrazolated bioactive compounds at a late stage, scaled up batches efficiently, and synthesized free amino-containing N-heterocycles via denitrogenation of tetrazoles.

Innovative cascade reaction for 2H-indazole derivative synthesis.

In the realm of synthetic organic chemistry, by using a one-pot sequential combination of MCR, it is possible to manufacture chemical commodities (fine chemicals, agrochemicals, and pharmaceutical substances) that enhance our quality of life while generating less waste materials and increasing economic advantages. With this motivation, using a "one-pot" method with multiple components, we present a relatively simple way to make stereoselective substitute 2H-indazole analogues for this study. Firstly, functionalised 3-bromo-4-((methylthio)methyl) derivatives were produced using DMSO as both a carbon source and a solvent, in conjunction with TMSOTf as the Lewis acid promoter. These derivatives were then utilised in the synthesis of 2-H-indazole derivatives with an up to 80% yield using t-Bu3PHBF4 as the ligand and Cs2CO3 as the base, in the presence of a Pd catalyst at 100°C in an airtight tube. The phenyl ring is endowed with an electron-releasing group situated at position C-6, which efficiently synthesises several 2-H-indazol derivatives with cost-efficient and noteworthy yields by using this method. A comparative analysis of a number of halogen derivatives was also undertaken, using a variety of solvents that were classified according to their halogen group. To confirm the structures of the synthesised target compounds, spectrometric analysis (1H NMR, 13C NMR, and LCMS) was performed.

Enantioselective nickel-catalyzed anodic oxidative dienylation and allylation reactions

Precision control of stereochemistry in radical reactions remains a formidable challenge due to the prevalence of incidental racemic background reactions resulting from undirected substrate oxidation in the absence of chiral induction. In this study, we devised an thoughtful approach—electricity-driven asymmetric Lewis acid catalysis—to circumvent this impediment. This methodology facilitates both asymmetric dienylation and allylation reactions, resulting in the formation of all-carbon quaternary stereocenters and demonstrating significant potential in the modular synthesis of functional and chiral benzoxazole-oxazoline (Boox) ligands. Notably, the involvement of chiral Lewis acids in both the electrochemical activation and stereoselectivity-defining radical stages offers innovative departures for designing single electron transfer-based reactions, significantly underscoring the relevance of this approach as a multifaceted and universally applicable strategy for various fields of study, including electrosynthesis, organic chemistry, and drug discovery.

Precise Modulation of CO2 Sorption in Ti8Ce2-Oxo Clusters: Elucidating Lewis Acidity of the Ce Metal Sites and Structural Flexibility.

Investigating the structure-property correlation in porous materials is a fundamental and consistent focus in various scientific domains, especially within sorption research. Metal oxide clusters with capping ligands, characterized by intrinsic cavities formed through specific solid-state packing, demonstrate significant potential as versatile platforms for sorption investigations due to their precisely tunable atomic structures and inherent long-range order. This study presents a series of Ti8Ce2-oxo clusters with subtle variations in coordinated linkers and explores their sorption behavior. Notably, Ti8Ce2-BA (BA denotes benzoic acid) manifests a distinctive two-step profile during the CO2 adsorption, accompanied by a hysteresis loop. This observation marks a new instance within the metal oxide cluster field. Of intrigue, the presence of unsaturated Ce(IV) sites was found to be correlated with the stepped sorption property. Moreover, the introduction of an electrophilic fluorine atom, positioned ortho or para to the benzoic acid, facilitated precise control over gate pressure and stepped sorption quantities. Advanced in situ techniques systematically unraveled the underlying mechanism behind this unique sorption behavior. The findings elucidate that robust Lewis base-acid interactions are established between the CO2 molecules and Ce ions, consequently altering the conformation of coordinated linkers. Conversely, the F atoms primarily contribute to gate pressure variation by influencing the Lewis acidity of the Ce sites. This research advances the understanding in fabricating metal-oxo clusters with structural flexibility and provides profound insights into their host-guest interaction motifs. These insights hold substantial promise across diverse fields and offer valuable guidance for future adsorbent designs grounded in fundamental theories of structure-property relationships.

Base-stabilized Gallium Sulfides and Selenides Supported by a Bis(oxazolinyl)(phenyl)methanide Ligand: Trapping Singly Base-Stabilized Gallium Chalcogenide.

Gallylene supported by a bis(oxazolinyl)(phenyl)methanide (Boxm) ligand was synthesized and structurally characterized. The reaction of this gallylene with triphenylphosphine sulfide/selenide yielded dimeric gallium sulfide and selenide. These compounds could be converted to monomeric terminal sulfide and selenide by coordination of an external Lewis base such as an N-heterocyclic carbene (NHC or IMe4) and 4-dimethylaminopyridiene (DMAP). These doubly-base-stabilized gallium sulfide/selenide reacted with phenyl isocyanate to give the corresponding cycloadducts by releasing the Lewis base, indicating the formation of a single-base-stabilized gallium sulfide/selenide intermediate.

Preparation of Magnetically Recyclable MIL‐101‐immobilized Frustrated Lewis Pairs for the Reduction of Aldehydes and Ketones

Frustrated Lewis pairs (FLPs), composed of spatially hindered Lewis acids and bases, are promising catalysts for the catalytic hydrogenation of unsaturated organic substrates, but the lack of reusability limits their development. The functionalization of solid materials with molecular FLP is a promising method for preparing heterogeneous FLP catalysts. In this work, a magnetically recyclable FLP catalyst was successfully prepared for the reductive carbonyl compounds to the corresponding alcohols. FLP of 2‐Ph2PPhCHO/B(C6F5)3 was grafted into NH2‐MIL‐101@Fe3O4 composite material through an aldehyde‐amine condensation reaction. The as‐prepared FLP‐NH‐MIL‐101@Fe3O4 exhibited remarkable catalytic activity for aldehyde/ketone carbonyl compounds. In addition, FLP‐NH‐MIL‐101@Fe3O4 displays outstanding magnetic recyclability and can be reused 8 times without loss of activity.

A Fast and Efficient Molecular Networking Approach for Reactivity of Natural Products Exploration in Plant Extracts: Application to Diterpene Esters from Euphorbia dendroides.

Natural products represent a rich source of bioactive compounds, covering a large chemical space. Even if challenging, this diversity can be extended by applying chemical modifications. However, these studies generally require multigram amounts of isolated natural products and face frequent testing failures. To overcome this limitation, we propose a rapid and efficient approach that uses molecular networking (MN) to visualize the new chemical diversity generated by simple chemical modifications of natural extracts. Moreover, the strategy deployed enables the most appropriate reagents to be defined quickly upstream of a reaction on a pure compound, in order to maximize chemical diversity. This methodology was applied to the latex extract of Euphorbia dendroides to follow the reactivity toward a series of Brønsted and Lewis acids of three class of diterpene esters identified in this species: jatrophane, terracinolide, and phorbol. Through the molecular networking interpretation, with the aim to illustrate our approach, BF3·OEt2 was selected for chemical modification on isolated jatrophane esters. Three rearranged compounds (3-5) were obtained, showing that the most appropriate reagents can be selected by MN interpretation.