Facile Cleavage Research Articles

Cleavage of a Peroxide Bond via a Dual Attack by Functional Mimics of Glutathione Peroxidase.

Nonmetal-containing peroxidase enzymes, including glutathione peroxidase (GPx), and peroxiredoxins, control cellular redox levels by catalyzing the reduction of H2O2. The remarkably higher reactivity of GPx enzyme as compared to the fully dissociated synthetic selenolate/thiolate molecule is probably due to the dual-attack on the peroxide bond (HO1-O2H) by the enzyme; The first one is a nucleophilic attack of the selenolate/thiolate moiety to O1 atom and the second attack at the O2 atom of the peroxide bond by the acidic "parked proton" from Trp or His residue present at the enzyme's active site, leading to the facile cleavage of O-O bond. Herein, we report two synthetic compounds (1 and 2), having a selenolate (Se-) and a proton donor (imidazolium or -COOH group) moieties, which showed excellent GPx-like activity via dual-attack on the peroxide bond. The combined effect of selenolate moiety that donates electrons to the antibonding (σ*) orbital of O1-O2 bond and the imidazolium or carboxylic acid moiety at the side chain that forms a strong H-bonding with the O2 atom facilitates O-O bond cleavage of H2O2 more efficiently. 1 and 2 exhibit remarkable ability in protecting Cu(I)-complex [TpmCu(CH3CN)]+ (9) against H2O2 by acting as a sacrificial antioxidant, thereby preventing metal-mediated ROS production.

High Spin-State Modulation of Catalytic Centers by Weak Ligand Field for Promoting Sulfur Redox Reaction in Lithium-Sulfur Batteries.

The spin state of transition-metal compounds in lithium-sulfur batteries (LSBs) significantly impacts the electronic properties and the kinetics of sulfur redox reactions (SRR). However, accurately designing the spin state remains challenging, which is crucial for understanding the structure-performance relationship and developing high-performance electrocatalysts. Herein, the CoF2, specifically the Co2+ with 3d7 electrons in a high-spin state distribution (t2g 5eg 2), were tailored predictably for the first time through the weak coordination field effect of the F element. Both DFT calculations and experimental results confirm that the spin state of Co2+ transitions from low- to high-spin configurations and strongly interacts with sulfur species through Co-S and Li-F bonds during the SRR process. This interaction weakens the S-S bond, promoting its facile cleavage from both ends while also facilitating the rapid and uniform nucleation of Li2S2/Li2S, thus resulting in LSBs with a capacity of 447.7 mAh g-1 at 10 C rates and stable cycling for 1000 cycles, with an acceptable practical capacity of 585 mAh g-1 at a high sulfur loading mass of 10 mg cm-2. This work achieves rational control of the active Co2+ d electron state through the field effect and enriches the application of spin control to accelerate SRR in LSBs.

Strikingly Facile Cleavage of N-H/N-O Bonds Induced by Surface Frustrated Lewis Pair on CeO2(110) to Boost NO Reduction by NH3.

Ceria with surface solid frustrated Lewis pairs (FLPs), formed by regulating oxygen vacancies, demonstrate remarkable ability in activating small molecules. In this work, we extended the application of FLPs on CeO2(110) to the selective catalytic reduction of NO by NH3 (NH3-SCR), finding a notable enhancement in performance compared to ordinary CeO2(110). Additionally, an innovative approach involving H2 treatment was discovered to increase the number of FLPs, thereby further boosting the NH3-SCR efficiency. Typically, NH3-SCR on regular CeO2 follows the Eley-Rideal (E-R) mechanism. However, density functional theory (DFT) calculations revealed a significant reduction in the energy barriers for the activation of N-O and N-H bonds under the Langmuir-Hinshelwood (L-H) mechanism with FLPs present. This transition shifted the reaction mechanism from the E-R pathway on regular R-CeO2 to the L-H pathway on FLP-rich FR-CeO2, as corroborated by the experimental findings. The practical application of FLPs was realized by loading MoO3 onto FLP-rich FR-CeO2, leveraging the synergistic effects of acidic sites and FLPs. This study provides profound insights into how FLPs facilitate N-H/N-O bond activation in small molecules, such as NH3 and NO, offering a new paradigm for catalyst design based on catalytic mechanism research.

Multielectron Reduction of Nitrosoarene via Aluminylene-Silylene Cooperation.

The cooperative effects of main-group elements pave the way for novel chemical transformations. However, the potential of bimetallic complexes featuring the most abundant aluminum and silicon elements remains largely unexplored. In this study, we present the synthesis and characterization of bis(silylene)-stabilized aluminylene 2. The cooperation between aluminylene and silylene allows for the facile cleavage of the N-O bond in nitrosoarenes, producing an aluminum imide complex 4 and tetracyclic oxazasilaalanes 5 and 6, and also promotes the dearomatization of 2-methylquinoline, yielding a silylalane 7. In addition, 2 is an effective precatalyst for the reductive coupling of nitrosoarenes to azoxyarenes. These results outline an approach for orchestrating aluminum and silicon cooperation to facilitate chemical bond activation.

Preferred Electric Field Mechanism for Frustrated Lewis Pair Reactivity.

This study employs computational methods to investigate the mechanism of H2 activation by frustrated Lewis pair (FLP) species, including both intermolecular and intramolecular nitrothane/borane FLP systems. Previous studies have proposed two qualitative reactivity mechanism models to explain the facile cleavage of H2 by FLPs. The findings of this study support the electric field mechanism as the favorable pathway for H2 cleavage. Utilizing frontier molecular orbital theory and energy decomposition analysis, the study explores the electronic structure and nature of the reactions under an external electric field (EEF). Analysis using the activation strain model highlights the significant influence of geometrical deformation energies of FLPs on the activation barriers of H2 activation reactions. Computational results suggest that H2 activation by FLP molecules follows the electric field mechanism, indicating the potential of the FLP/EEF combination as an effective activator for inert molecules.

Hydrogenolysis of Cationic Half-Sandwich Zinc Complexes Containing a Chelating Amine: Facile Cleavage of Zinc-Carbon Bond by Dihydrogen to Give Zinc Hydride Cations.

Cationic half-sandwich zinc complexes containing chelating amines [Cp*Zn(Ln)][BAr4 F] (2 a, Cp*=η3-C5Me5, Ln=N,N,N',N'-tetramethylethylenediamine, TMEDA; 2 b, Ln=N,N,N',N'-tetraethylethylenediamine, TEEDA; 2 c, Cp*=η1-C5Me5, Ln=N,N,N',N'',N''-pentamethyldiethylenetriamine, PMDTA; Ar4 F=(3,5-(CF3)2C6H3)4) reacted with dihydrogen (ca. 2 bar) in THF at 80 °C to give molecular zinc hydride cations [(Ln)ZnH(thf)m][BAr4 F] (3 a,b, m=1; 3 c, m=0) previously reported along with Cp*H. Pseudo first-order kinetics with respect to the concentration of 2 b suggests heterolytic cleavage of dihydrogen by the Zn-Cp* bond, reminiscent of σ-bond metathesis. Hydrogenolysis of the zinc cation 2 b in the presence of benzophenone gave the zinc alkoxide [(TEEDA)Zn(OCHPh2)(thf)][BAr4 F] (5 b). Cation 2 b was shown to catalytically hydrogenate N-benzylideneaniline. The PMDTA complex 2 c underwent C-H bond activation in acetonitrile to give a dinuclear μ-κC,κN-cyanomethyl zinc complex [(PMDTA)Zn(CH2CN)]2[BAr4 F]2 (6 c).

Conformers influence on UV-absorbance of avobenzone

Avobenzone is most commonly used FDA approved chemical UV-A filter in many sunscreen formulations. An important drawback of avobenzone is its photounstability and undergoes chemical transformation upon exposure to UV-radiation/sunlight. Eventhough single bond rotations are implicated in the radiation induced chemical modification of avobenzone, the conformers role of avobenzone on UV absorbance is yet to be addressed. Using the In silico platform working on Density Functional Theory (DFT), the communication evaluates the role of conformers on UV absorbance spectra of enol/keto forms of avobenzone. The results indicate that the conformers of enolic-form of avobenzone have broad range of absorbance from 273-389 nm and the keto-form has relatively narrow range of absorbance from 266-288 nm. The chelated conformers of enolic-avobenzone with intramolecular hydrogen bond are swingy in nature yet possessing strong bond contributing to its broad-spectrum UVA filtering activity. Among the conformers of keto-form of avobenzone, the planar conformer with the torsional angle 180° undergo facile Norrish Type-I cleavage. Mapping of the data with previous experimental results has allowed identifying 3D structures involved in the key steps of photoketonization process of avobenzone. The reported results may help to understand the molecular basis of enol-to-keto photochemical transformation of avobenzone and to develop photostabilizer to endure long-lasting photoprotection to avobenzone.

Pd nanoflakes epitaxially grown on defect MoS2 nanosheets for enhanced nitroarenes hydrogenation to anilines

Hydrogenation of nitroarenes to anilines under mild conditions is attractive from both theoretical and practical viewpoints. Here, high-performance catalyst with layered Pd nanoparticles epitaxially growing on ultrathin MoS2 nanosheets (Pd/MoS2) were prepared. It shows surprisingly high catalytic activity, selectivity and stability for hydrogenation of various nitroarenes to corresponding anilines; the turnover frequency is one or two magnitudes higher than conventional Pd-based catalysts. Surface sulfur vacancies are formed on MoS2 nanosheets with low formation energy barrier. These S vacancies provide efficient positions for adsorbing Pd atoms, which enables facile cleavage of N–O bond as result of strong interfacial electron interaction that decreases activation energy by 0.41 eV in comparison with conventional Pd catalysts. In situ spectroscopy and DFT calculation results reveal a dual-site mechanism, in which surface Pd sites adsorb and dissociate H2 into active H*, and then readily reacts with nearby activated nitroarene to form aniline on interfacial Pd-MoS2 sites.

Synthesis and Photolysis Properties of a New Chloroquine Photoaffinity Probe.

A new chloroquine-derived photoaffinity probe has been prepared by a convergent synthesis from derivative of 4,7-dichloroquinoline and N1,N1-diethyl-N4-methylpentane. The features of this probe are a unique 3-azido photolabel, the pyridine ring of the quinoline, and the presence of a secondary amine at the 4-position of the quinoline. These features, particularly the 4-amino methylation, prevent triazole formation through combination of the 3-azide and the 4-amine. This undergoes facile cleavage with exposure to a medium-pressure mercury lamp with a 254 nm excitation wavelength. Trapping of the nitrene byproduct is accomplished with its reaction with N-phenylmaleimide as its cycloazidation product. The structure of a ring-opened DBU amine has been structurally characterized.

Fine-Scale Characterization of Plant Diterpene Glycosides Using Energy-Resolved Untargeted LC-MS/MS Metabolomics Analysis.

Plant diterpene glycosides are essential for diverse physiological processes. Comprehensive structural characterization proved to be a challenge due to variations in glycosylation patterns, diverse aglycone structures, and the absence of comprehensive reference databases. In this study, a method for fine-scale characterization was proposed based on energy-resolved (ER) untargeted LC-MS/MS metabolomics analysis using steviol glycosides as a demonstration. Energy-dependent fragmentation patterns were unveiled by a series of model compounds. Distinct glycosylation sites were discerned by leveraging varying fragmentation energies for the precursor ions. The sugar moiety linkage at C19OOH (R1) exhibited facile and intact cleavage at low collision energies, while the sugar moiety at C13-OH (R2) demonstrated consecutive cleavage with increasing energy. Aglycone ions exhibited a higher relative intensity at NCE 50, with relative intensities ranging from 95% to 100%. Subsequently, aglycone candidates, R1 sugar composition, and R2 sugar sequence were deduced through ER-MS/MS analysis. The developed method was applied to Stevia rebaudiana leaves. A total of 91 diterpene glycosides were unambiguously identified, including 16 steviol glycosides with novel acetylglycosylation patterns. This method offers a rapid alternative for glycan analysis and the structural differentiation of isomers. The developed method enhances the understanding of diterpene glycosides in plants, providing a reliable tool for the in-depth characterization of complex metabolite profiles.

Polar X-H Bond (X=O, S, N) Activation at a Cage Silanide.

Low-valent silicon compounds such as neutral silylenes display versatile reactivity for the activation of small molecules. In contrast, their anionic congeners silanides ([R3 Si- ]) have primarily been investigated for their nucleophilic reactivity. Here we show that incorporating a silanide center in a bicyclic cage structure allows for formal oxidative addition of polar element-hydrogen bonds (RX-H, R=aromatic residue, X=O, S, NH). The resulting hydrosilicates were isolated and characterized structurally and spectroscopically. Density Functional Theory (DFT) calculations and experimental observations support an ionic mechanism for RX-H bond activation. Finally, the reactivity of the RS-H bond adduct was further investigated, revealing that it behaves as a Lewis pair upon facile heterolytic cleavage of the Si-S bond.

Polar X–H Bond (X = O, S, N) Activation at a Cage Silanide

Low‐valent silicon compounds such as neutral silylenes display versatile reactivity for the activation of small molecules. In contrast, their anionic congeners silanides ([R3Si–]) have primarily been investigated for their nucleophilic reactivity. Here we show that incorporating a silanide center in a bicyclic cage structure allows for formal oxidative addition of polar element‐hydrogen bonds (RX–H, R = aromatic residue, X = O, S, NH). The resulting hydrosilicates were isolated and characterized structurally and spectroscopically. Density Functional Theory (DFT) calculations and experimental observations support an ionic mechanism for RX–H bond activation. Finally, the reactivity of the RS–H bond adduct was further investigated, revealing that it behaves as a Lewis pair upon facile heterolytic cleavage of the Si–S bond.

Coordination-induced bond weakening and small molecule activation by low-valent titanium complexes.

Bond activation of small molecules through coordination to low valent metal complexes in M⋯X-H type interactions (where X = O, N, B, Si, etc.) leads to the formation of unusually weak X-H bonds and provides a powerful approach for the synthesis of target compounds under very mild conditions. Coordination of small molecules like water, amides, silanes, boranes, and dinitrogen to Ti(III) or Ti(II) complexes results in the synergetic redistribution of electrons between the metal orbitals and the ligand orbitals which weakens and enables the facile cleavage of the X-H or N-N bonds of the ligands. This review presents an overview of coordination-induced bond activation of small molecules by low valent titanium complexes. In particular, the applications of low valent titanium-induced bond weakening in nitrogen fixation are presented. The review concludes with potential future directions for work in this area including low-valent Ti-based PCET systems, photocatalytic nitrogen reduction, and approaches to tailoring complexes for optimal bond activation.

Evidence for a kinetic FLP reaction pathway in the activation of benzyl chlorides by alkali metal-phosphine pairs.

Kinetic frustrated Lewis pairs (FLP) allow facile cleavage of a number of E-H bonds (E = H, Si, C, B) where both the Lewis base and Lewis acid are involved in the bond activation transition state. More recently, kinetic FLP systems have been extended to the cleavage of C-X (X = F, Cl, Br) bonds. We report on the role of sodium tetrakis(pentafluorophenyl)borate in the benzylation of triarylphosphines, where the sodium cation and phosphine support a kinetic FLP type transition state.

Access to NHC-Boryl Mono- and Bis-Selenide and Utility as Mild Selenium Transfer Reagent Including to the C-F Bond.

Reactions of 5-SIDipp ⋅ BH3 (5-SIDipp=1,3-bis(2,6-diisopropylphenyl)-imidazolin-2-ylidene) (1) with diphenyldiselenide provide access to 5-SIDipp-boryl mono- (5-SIDipp ⋅ BH2 SePh) (2) and bis-selenide (5-SIDipp ⋅ BH(SePh)2 ) (3). The facile cleavage of the B-Se bond makes 2 a neutral source of selenium nucleophiles in substitutions reactions with benzyl bromides, and provide access to the corresponding selenoethers. The direct transformations of one of the C(sp2 )-F bonds of C5 F5 N and C6 F5 CF3 to C-Se bonds have also been achieved by the use of 2 without employing transition-metal catalysts. While it was previously established that C6 F6 could undergo complete defluoroselenation under harsh conditions, we successfully achieved partial defluorination of C6 F6 by employing 2 as a mild selenide transfer reagent. During the formation of C-Se bonds through the cleavage of C-F bonds, the potential by-product NHC ⋅ BH2 F undergoes ring expansion of the NHC, leading to the formation of the six-membered diaazafluoroborinane (7).

Role of inorganic anions in improving the oxidizing capacity of heat-activated peroxymonosulfate: Identification of primary degradative pathways

This study demonstrated a drastic improvement in the oxidizing capacity of heat-activated peroxymonosulfate (heat/PMS) upon the addition of bicarbonate (HCO3) and phosphate (PO4). Injecting the anions caused a 20- to 30-fold increase in the phenol degradation efficiency of heat/PMS at the temperature range of 40–50 ℃ that was insufficient to thermally activate peroxydisulfate (PDS). The heat/PMS-PO4 outperformed heat/PDS in degrading benzoic acid, whereas heat/PMS-HCO3 marginally decomposed it. The reactivity of heat/PMS-PO4 did not vary sensitively depending on substrate type, which resulted from the increased yield of sulfate radical due to facile thermal cleavage of the peroxide bond loosened in the PMS-PO4 complex, based on the electron paramagnetic spectral features and quenching effects of radical scavengers. Degradation of phenols and furfuryl alcohol by heat/PMS-anion was highly accelerated under alkaline conditions through heat-promoted direct PMS oxidation and singlet oxygenation. Along with the similarity between the heat/PMS-anion systems in intermediate distribution (distinguished from that of heat/PDS) and chronoamperometric current response of the heated PMS solution upon the subsequent injection of anion and phenol, the extent of PMS consumption in the heated PMS-anion or PMS-organic-anion mixtures, which depended on substrate type and temperature, implied the role of heat-activated PMS-anion complexes as the non-radical oxidants.

Cooperative Bond Activation and Catalytic CO2 Functionalization with a Geometrically Constrained Bis(silylene)-Stabilized Borylene

Metal-ligand cooperativity has emerged as an important strategy to tune the reactivity of transition-metal complexes for the catalysis and activation of small molecules. Studies of main-group compounds, however, are scarce. Here, we report the synthesis, structural characterization, and reactivity of a geometrically constrained bis(silylene)-stabilized borylene. The one-pot reaction of [(SiNSi)Li(OEt2)] (SiNSi = 4,5-bis(silylene)-2,7,9,9-tetramethyl-9H-acridin-10-ide) with 1 equiv of [BBr3(SMe2)] in toluene at room temperature followed by reduction with 2 equiv of potassium graphite (KC8) leads to borylene [(SiNSi)B] (1), isolated as blue crystals in 45% yield. X-ray crystallography shows that borylene (1) has a tricoordinate boron center with a distorted T-shaped geometry. Computational studies reveal that the HOMO of 1 represents the lone pair orbital on the boron center and is delocalized over the Si-B-Si unit, while the geometric perturbation significantly increases its energy. Borylene (1) shows single electron transfer reactivity toward tris(pentafluorophenyl)borane (B(C6F5)3), forming a frustrated radical pair [(SiNSi)B]•+[B(C6F5)3]•-, which can be trapped by its reaction with PhSSPh, affording an ion pair [(SiNSi)BSPh][PhSB(C6F5)3] (3). Remarkably, the cooperation between borylene and silylene allows the facile cleavage of the N-H bond of aniline, the P-P bond in white phosphorus, and the C═O bond in ketones and carbon dioxide, thus representing a new type of main-group element-ligand cooperativity for the activation of small molecules. In addition, 1 is a strikingly effective catalyst for carbon dioxide reduction. Computational studies reveal that the cooperation between borylene and silylene plays a key role in the catalytic chemical bond activation process.

Facile and dynamic cleavage of every iron–sulfide bond in cuboidal iron–sulfur clusters

Nature employs weak-field metalloclusters to support a wide range of biological processes. The most ubiquitous metalloclusters are the cuboidal Fe-S clusters, which are comprised of Fe sites with locally high-spin electronic configurations. Such configurations enhance rates of ligand exchange and imbue the clusters with a degree of structural plasticity that is increasingly thought to be functionally relevant. Here, we examine this phenomenon using isotope tracing experiments. Specifically, we demonstrate that synthetic [Fe4S4] and [MoFe3S4] clusters exchange their Fe atoms with Fe2+ ions dissolved in solution, a process that involves the reversible cleavage and reformation of every Fe-S bond in the cluster core. This exchange is facile-in most cases occurring at room temperature on the timescale of minutes-and documented over a range of cluster core oxidation states and terminal ligation patterns. In addition to suggesting a highly dynamic picture of cluster structure, these results provide a method for isotopically labeling pre-formed clusters with spin-active nuclei, such as 57Fe. Such a protocol is demonstrated for the radical S-adenosyl-l-methionine enzyme, RlmN.

Nonionic, Cleavable Surfactant for Top-Down Proteomics.

Nonionic surfactants are often used as general reagents for cell lysis enabling protein extraction, stabilization, and purification under nondenaturing conditions for downstream analysis in structural biology. However, the presence of surfactants in the sample matrix often has a deleterious effect on electrospray ionization (ESI)-mass spectrometry (MS) analysis of proteins and complexes. Here, we report a nonionic, cleavable surfactant, n-decyl-disulfide-β-D-maltoside (DSSM), for top-down proteomics. DSSM was designed to mimic the properties of one of the most common surfactants used in structural biology, n-dodecyl-β-D-maltoside (DDM), but contains a disulfide bond that allows for facile cleavage and surfactant removal before or during MS analysis. We have shown that DSSM is compatible with direct electrospray ionization (ESI)-MS analysis and reversed-phase liquid chromatography (RPLC)-MS analysis of proteins and protein complexes. We have demonstrated that DSSM can facilitate top-down proteomic characterization of membrane proteins such as a model ion channel protein and a G protein-coupled receptor as well as endogenous proteins from cell lysates for the determination of sequence variations and posttranslational modifications (PTMs). Conceivably, DSSM could serve as a general replacement for DDM in proteomic experiments and structural biology studies.

A Free Phosphaborene Stable at Room Temperature.

Free phosphaborenes (R-P═B-R) are PB analogues of alkynes, and their isolation is a long-sought-after goal. Herein, we demonstrate that the combination of a π-donating and a π-accepting substituent with bulky flanking arene rings enables the isolation of a crystalline free phosphaborene 5 at room temperature. This electron push-pull cooperation, combined with the kinetic protection, hinders its inherent tendency to oligomerize. This species features a PB double bond consisting of a conventional σ bond and a delocalized π bond. The lone pair of electrons at P slightly contributes to the PB bonding. Preliminary reactivity studies show that 5 undergoes facile (cyclo)addition reactions with p-methyl benzaldehyde, p-fluoroacetophenone, and carbon disulfide, the last of which results in facile PB double bond cleavage. Our strategy has a significant impact on the future synthesis of ambiphilic heterodiatomic multiply bonded main group species.