Heterolytic Bond Research Articles

Highly selective synthesis of surface FeIV=O with nanoscale zero-valent iron and chlorite for efficient oxygen transfer reactions

High-valent iron-oxo species (FeIV=O) has been a long-sought-after oxygen transfer reagent in biological and catalytic chemistry but suffers from a giant challenge in its gentle and selective synthesis. Herein, we propose a new strategy to synthesize surface FeIV=O (≡FeIV=O) on nanoscale zero-valent iron (nZVI) using chlorite (ClO2-) as the oxidant, which possesses an impressive ≡FeIV=O selectivity of 99%. ≡FeIV=O can be energetically formed from the ferrous (FeII) sites on nZVI through heterolytic Cl-O bond dissociation of ClO2- via a synergistic effect between electron-donating surface ≡FeII and proximal electron-withdrawing H2O, where H2O serves as a hydrogen-bond donor to the terminal O atom of the adsorbed ClO2- thereby prompting the polarization and cleavage of Cl-O bond for the oxidation of ≡FeII toward the final formation of ≡FeIV=O. With methyl phenyl sulfoxide (PMS16O) as the probe molecule, the isotopic labeling experiment manifests an exclusive 18O transfer from Cl18O2- to PMS16O18O mediated by ≡FeIV=18O. We then showcase the versatility of ≡FeIV=O as the oxygen transfer reagent in activating the C-H bond of methane for methanol production and facilitating selective triphenylphosphine oxide synthesis with triphenylphosphine. We believe that this new ≡FeIV=O synthesis strategy possesses great potential to drive oxygen transfer for efficient high-value-added chemical synthesis.

Stabilization of Carbocation Intermediate by Cucurbit[7]uril Enables High Photolysis Efficiency.

A cucurbit[7]uril-based host-guest strategy is employed to enhance the efficiency of photolysis reactions that release caged molecules from photoremovable protecting groups. The photolysis of benzyl acetate follows a heterolytic bond cleavage mechanism, thereby leading to the formation of a contact ion pair as the key reactive intermediate. The Gibbs free energy of the contact ion pair is lowered by 3.06 kcal/mol through the stabilization of cucurbit[7]uril, as revealed by DFT calculations, which results in a 40-fold increase in the quantum yield of the photolysis reaction. This methodology is also applicable to the chloride leaving group and the diphenyl photoremovable protecting group. We anticipate that this research presents a novel strategy to improve reactions involving active cationics, thereby enriching the field of supramolecular catalysis.

Noncovalent Modulation of Chemoselectivity in the Gas Phase Leads to a Switchover in Reaction Type from Heterolytic to Homolytic to Electrocyclic Cleavage.

Inthe gas phase, thermal activation of supramolecular assemblies such as host-guest complexes leads commonly to noncovalent dissociation into the individual components. Chemical reactions, for example of encapsulated guest molecules, are only found in exceptional cases. As observed by mass spectrometry, when 1-amino-methyl-2,3-diazabicyclo[2.2.2]oct-2-ene (DBOA) is complexed by the macrocycleb-cyclodextrin, its protonated complex undergoes collision-induced dissociation into its components, the conventional reaction pathway. Inside the macrocyclic cavity of cucurbit[7]uril (CB7), a competitive chemical reaction of monoprotonated DBOA takes place upon thermal activation, namely a stepwise homolytic covalent bond cleavage with the elimination of N2, while the doubly protonated CB7•DBOA complex undergoes an inner-phase elimination of ethylene, a concerted, electrocyclic ring-opening reaction. These chemical reaction pathways stand in contrast to the gas-phase chemistry of uncomplexed monoprotonated DBOA, for which an elimination of NH3predominates upon collision-induced activation, as a heterolytic bond cleavage reaction. The combined results, which can be rationalized in terms of organic-chemical reaction mechanisms and density-function theoretical calculations, demonstrate that chemical reactions in the gas phase can be steered chemoselectively through noncovalent interactions.

Noncovalent Modulation of Chemoselectivity in the Gas Phase Leads to a Switchover in Reaction Type from Heterolytic to Homolytic to Electrocyclic Cleavage

AbstractIn the gas phase, thermal activation of supramolecular assemblies such as host–guest complexes leads commonly to noncovalent dissociation into the individual components. Chemical reactions, for example of encapsulated guest molecules, are only found in exceptional cases. As observed by mass spectrometry, when 1‐amino‐methyl‐2,3‐diazabicyclo[2.2.2]oct‐2‐ene (DBOA) is complexed by the macrocycle β‐cyclodextrin, its protonated complex undergoes collision‐induced dissociation into its components, the conventional reaction pathway. Inside the macrocyclic cavity of cucurbit[7]uril (CB7), a competitive chemical reaction of monoprotonated DBOA takes place upon thermal activation, namely a stepwise homolytic covalent bond cleavage with the elimination of N2, while the doubly protonated CB7⋅DBOA complex undergoes an inner‐phase elimination of ethylene, a concerted, electrocyclic ring‐opening reaction. These chemical reaction pathways stand in contrast to the gas‐phase chemistry of uncomplexed monoprotonated DBOA, for which an elimination of NH3 predominates upon collision‐induced activation, as a heterolytic bond cleavage reaction. The combined results, which can be rationalized in terms of organic‐chemical reaction mechanisms and density‐function theoretical calculations, demonstrate that chemical reactions in the gas phase can be steered chemoselectively through noncovalent interactions.

A High‐Valent Ru−PCP Pincer Catalyst for the Hydrogenation of Organic Carbonates

AbstractIn this communication, we report on the successful application of a high‐valent RuIV bifunctional catalyst (1) for mild hydrogenation of cyclic and acyclic carbonates. Our experimental and theoretical studies suggest that the hydrogenation mechanism is operated by an unusual formally zwitterionic RuIV complex. According to our hypothesis, the positively charged high‐valent metal center is responsible for stronger hydrogen coordination. On the other hand, the proximate negatively charged ligand site facilitates heterolytic H2 bond activation, which leads to efficient catalysis.

Assessing Combinations of B(C6 F5 )3 and N2 -Derived Molybdenum Nitrido Complexes for Heterolytic Bond Activation.

Two different dinitrogen-derived molybdenum nitrido complexes varying by their geometry, ligand spheres and oxidations states were shown to engage their N ligand in dative bonding with the strong Lewis acid B(C6 F5 )3 . The stable adducts were assessed for frustrated Lewis pair-type heterolytic E-H bond splitting of hydrosilanes (E=Si) and HB(C6 F5 )2 . Whereas Si-H bond activation was achieved, HB(C6 F5 )2 was shown to substitute B(C6 F5 )3 in a quantitative or equilibrated fashion, depending on the nature of the nitrido complex. No B-H bond splitting was observed. Thermodynamics of these reactions, computed by DFT, are in agreement with the experimental outcomes.

Methane C–H bond heterolysis versus homolysis on Cu-MFI and Au-MFI

The methane activation reaction is of fundamental importance for its transformation into high-value chemicals. Despite the fact that both homolysis and heterolysis are competitive mechanisms of C-H scission, experimental and DFT studies have revealed heterolytic scission of the C-H bond over metal-exchange zeolites. To rationalize the new catalysts, work must be done on the homolytic versus heterolytic scission of the C-H bond mechanism on these catalysts. We have performed the quantum mechanical calculations for the C-H bond homolysis versus heterolysis over Au-MFI and Cu-MFI catalysts. Calculations results showed that homolysis of the C-H bond is favorable both thermodynamically as well as kinetically over Au-MFI catalysts. However, over Cu-MFI, heterolytic scission is favorable. Both Cu(I) and Au(I) activate the CH4 via electronic density back donation from filled nd10 orbitals, according to NBO calculations. Cu(I) cation has a higher electronic density back donation than Au(I) cation. This is also supported by the charge on the C-atom of Methane. Additionally, a greater negative charge on the O-atom in the active site in case of Cu(I), where proton transfer occurs, promotes heterolytic scission. Because of the larger size of the Au-atom and the smaller negative charge of the O-atom in the active site, where proton transfer occurs, C-H bond homolytic fission is preferable over Au-MFI.

Ultrasmall amorphous zirconia nanoparticles catalyse polyolefin hydrogenolysis

Carbon–carbon bond cleavage reactions, adapted to deconstruct aliphatic hydrocarbon polymers and recover the intrinsic energy and carbon value in plastic waste, have typically been catalysed by metal nanoparticles or air-sensitive organometallics. Metal oxides that serve as supports for these catalysts are typically considered to be inert. Here we show that Earth-abundant, non-reducible zirconia catalyses the hydrogenolysis of polyolefins with activity rivalling that of precious metal nanoparticles. To harness this unusual reactivity, our catalytic architecture localizes ultrasmall amorphous zirconia nanoparticles between two fused platelets of mesoporous silica. Macromolecules translocate from bulk through radial mesopores to the highly active zirconia particles, where the chains undergo selective hydrogenolytic cleavage into a narrow, C18-centred distribution. Calculations indicated that C–H bond heterolysis across a Zr–O bond of a Zr(O)2 adatom model for unsaturated surface sites gives a zirconium hydrocarbyl, which cleaves a C–C bond via β-alkyl elimination.

Thermal N–O bond heterolysis of TEMPO-CF2CF3 towards trifluoroacetylation of alcohols and amines

A perfluoroalkoxyamine TEMPO-CF2CF3 can be synthesized on gram-scale and it undergoes unusual N–O bond heterolytic cleavage under thermal conditions.

Pd−X Bond Homolysis Dissociation Free Energy (BDFE) Scales of [(tmeda)Pd(4‐F−C6H4)X] (X=OR, NHAr) in DMSO

AbstractTransition metal intermediates bearing M−X σ‐bonds are ubiquitous in metal‐mediated C−X bond transformations. Thermodynamic knowledge of M−X bond cleavage is crucial to explore relevant reactions; but little was accumulated till present due to lack of suitable determination methods. We here report the first systematic study of the Pd−X bond homolysis dissociation free energies [BDFE(Pd−X)] of representative [(tmeda)Pd(4‐F−C6H4)X] (tmeda=N,N,N′,N′‐tetramethylethylenediamine, X=OR or NHAr) in DMSO on the basis of reliable measurement of their bond heterolysis energies (ΔGhet(Pd−X)). Despite ΔGhet(Pd−O)s of palladium‐phenoxides are generally found about 8 kcal/mol smaller than ΔGhet(Pd−N)s of palladium‐amidos, their BDFE(Pd−X)s are observed comparable. The structure‐property relationship was investigated to disclose an enhancement effect of electron‐withdrawing groups on BDFE(Pd−X)s. Linear free energy relationship analysis revealed that Pd−X bonds are more sensitive than X−H bonds to structural variation. The energetic propensity of reductive elimination from arylpalladium complexes was evaluated by combinatorial use of BDFE(Pd−X)s and BDFE(C−X)s, indicating an overall thermodynamic bias to C−N bond formation.

Evaluating the predictive character of the method of constrained geometries simulate external force with density functional theory

Mechanochemistry is a fast-developing field of interdisciplinary research with a growing number of applications. Therefore, many theoretical methods have been developed to quickly predict the outcome of mechanically induced reactions. Constrained geometries simulate External Force (CoGEF) is one of the earlier methods in this field. It is easily implemented and can be conducted with most DFT codes. However, recently, we observed totally different predictions for model systems of epoxy resins in different conformations and with different density functionals. To better understand the conformational and functional dependence in typical CoGEF calculations we present a systematic evaluation of the CoGEF method for different model systems covering homolytic and heterolytic bond cleavage reactions, electrocyclic ring opening reactions and scission of non-covalent interactions in hydrogen-bond complexes. From our calculations we observe that many mechanochemical descriptors strongly depend on the functional used, however, a systematic trend exists for the relative maximum Force. In general, we observe that the CoGEF procedure is forcing the system to high energetic regions on the molecular potential energy profiles, which can lead to unexpected and uncorrelated predictions of mechanochemical reactions. This is questioning the true predictive character of the method.

How Do Preorganized Electric Fields Function in Catalytic Cycles? The Case of the Enzyme Tyrosine Hydroxylase.

Nature has devised intrinsic electric fields (IEFs) that are engaged in electrostatic catalysis of enzymes. But, how does the IEF target its function in enzymes that involve several reaction steps in catalytic cycles? To decipher the impact of the IEF on the catalytic cycle of an enzyme system, we have performed molecular dynamics and quantum-mechanical/molecular-mechanical (QM/MM) simulations on tyrosine hydroxylase (TyrH). The catalytic cycle of TyrH involves two reaction stages: the activation of H2O2 to form the active species of compound I (Cpd I), in the first stage, and the Cpd I-mediated hydroxylation of l-tyrosine to l-DOPA, in the second stage. For the first stage, the QM/MM calculations show that a heme-propionate group functions as a base to catalyze the O-O heterolysis reaction. For the second stage, the study reveals that the reaction is initiated by the His88-mediated proton-coupled electron transfer followed by the oxygen atom transfer from compound II (Cpd II) to the l-Tyr substrate. Importantly, our calculations demonstrate that the IEF in TyrH is optimized to promote the O-O bond heterolysis that generates the active species of the enzyme, Cpd I. However, the same IEF slows down the subsequent aromatic hydroxylation. Thus, the IEF in the TyrH enzymes does not catalyze the product formation step, but will selectively boost one or more challenging steps in the catalytic cycle. These findings have general implications on O2/H2O2-dependent metalloenzymes, which can expand our understanding of how nature has used electric fields as "smart reagents" in modulating the catalytic reactivity.

Boosting propane purification on Pt/ZrOSO4 nanoflowers: Insight into the roles of different sulfate species in synergy with Pt

Herein, ZrOSO4 nanoflowers with high sulfates content and the coexistence of (SO3)ad and SO42- species has been developed as the support of Pt-based catalysts for propane combustion. Compared with the Pt catalysts supported on conventional sulfated-ZrO2 and ZrO2, the Pt/ZrOSO4 gives the highest specific reaction rate of 355 μmol gPt−1 s−1 at 190 °C, the TOF value on Pt/ZrOSO4 is 2 times of that on Pt/sulfated-ZrO2 and 7 times of that on Pt/ZrO2. Differentfrom that only SO42- on the Pt/sulfated-ZrO2, there are two sulfate species on the Pt/ZrOSO4, conventional SO42- and (SO3)ad. The presence of sulfates not only leads to the formation of Brønsted acid sites and promotes the propane adsorption, but also significantly affects the chemical states of Pt species. The interaction between Pt and SO42- results in the formation of reactive Pt0 species, which facilitates the CC bond activation, and the Pt-(SO3)ad electronic interaction is beneficial for the generation of the metastable Pt+, which further promotes propanecombustion via heterolytic CH bond activation. Moreover, the Pt/ZrOSO4 also can provide active oxygen species with enhanced oxygen mobility and reactivity due to the presence of Pt-O-SO3 species, which can accelerate the oxidation of reaction intermediates. This workcontributes to in-depth insight into the role of different sulfate species for propane combustion over Pt-based catalysts.

Coordination-Induced Weakening of a C(sp3)-H Bond: Homolytic and Heterolytic Bond Strength of a CH-Ni Agostic Interaction.

The scission of a C(sp3)-H bond to form a new metal-alkyl bond is a fundamental step in coordination chemistry and catalysis. However, the extent of C-H bond weakening when this moiety interacts with a transition metal is poorly understood and quantifying this phenomenon could provide insights into designing more efficient C-H functionalization catalysts. We present a nickel complex with a robust adamantyl reporter ligand that enables the measurement of C-H acidity (pKa) and bond dissociation free energy (BDFE) for a C(sp3)-H agostic interaction, showing a decrease in pKa by dozens of orders of magnitude and BDFE decrease of about 30 kcal/mol upon coordination. X-ray crystallographic data is provided for all molecules, including a distorted square planar NiIII metalloradical and "doubly agostic" NiII(κ2-CH2) complex.

A High-Valent Ru-PCP Pincer Catalyst for Hydrogenation of Carbonyl and Carboxyl Compounds under Molecular Hydrogen.

Low-valent metals traditionally dominate the domain of catalytic hydrogenation. However, metal-ligand cooperating (MLC) catalytic systems, operating through heterolytic H-H bond splitting by a Lewis acidic metal and a basic ligand site, do not require an electron-rich metal. On the contrary, high-valent metals that induce weaker back donation facilitate heterolytic bond activation. Here we report, for the first time, the efficient hydrogenation of carbonyl and carboxyl compounds under molecular hydrogen catalyzed by a structurally well-defined RuIV catalyst bearing a bifunctional PCP pincer ligand. The catalyst exhibits reactivity toward molecular hydrogen superior to that of the low-valent analog and allows hydrogen activation even at room temperature.

A Perspective on the Force-Induced Heterolytic Bond Cleavage in Triarylmethane Mechanophores

AbstractTriarylmethane derivatives and their corresponding trityl carbocations are among the oldest chemical species synthesized and studied by chemists. The carbocationic platforms are particularly interesting due to their stability, high extinction coefficient, and tunable absorption of light in the visible spectrum, which can be achieved through structural modifications. These stable cations are traditionally obtained through heterolytic cleavage of judiciously designed, parent triarylmethanes by exposure to acids or UV light (λ < 300 nm), and methods based on electrochemistry or radiolysis. Our group has recently discovered that trityl carbocations can be generated also via mechanical stimulation of solid polymer materials featuring triarylmethane units as covalent crosslinks. In this Synpacts contribution, we expand on our previous finding by discussing some intriguing research questions that we aim to tackle in the immediate future.1 Introduction2 The Development of Our First Triarylmethane Mechanophore3 The Potential Reversibility of Triarylmethane Mechanophores4 A General Molecular Platform for Force-Induced, Scissile, Homolytic and Heterolytic Bond Cleavage?5 Conclusion

A Distinctive Pattern for Substituent Effects on Transition Metal Centers: Enhanced Electron-Donating Capacity of Cationic Palladium Species

A Distinctive Pattern for Substituent Effects on Transition Metal Centers: Enhanced Electron-Donating Capacity of Cationic Palladium Species

Computational study on the mechanism of metal‐free photochemical borylation of aryl halides

AbstractC‐radical borylation is a significant approach for the construction of carbonboron bond. Photochemical borylation of aryl halides successfully applied this strategy. However, precise mechanisms, such as the generation of aryl radicals and the role of base additive (TMDAM) and water, remain controversy in these reactions. In this study, photochemical borylation of aryl halides has been researched by density functional theory (DFT) calculations. Indeed, the homolytic cleavage of the CX bond under irradiation with UV‐light is a key step for generation of aryl radicals. Nevertheless, the generation of aryl radicals may also undergo the process of single electron transfer and the heterolytic carbonhalogen bond cleavage sequence, and the latter is favorable during the reaction.

Cluster Model Study into the Catalytic Mechanism of α-Ketoglutarate Biodegradation by the Ethylene-Forming Enzyme Reveals Structural Differences with Nonheme Iron Hydroxylases

Ethylene is an important signaling molecule in plants that triggers the growth of leaves, flowers, and fruits. One of the enzymes involved in the biosynthesis of ethylene is the ethylene-forming enzyme (EFE), which is an usual nonheme iron enzyme that biodegrades α-ketoglutarate into three CO2 molecules and ethylene. As the detailed mechanism of EFE in the biosynthesis of ethylene remains controversial and particularly the function of the co-substrate l-arginine, we decided to pursue a density functional theory study on the possible pathways of the enzyme leading to ethylene biosynthesis and test many possible pathways and mechanisms. A large active site cluster model of 322 atoms was created, which contains all the features of the first- and second-coordination sphere of the active site and substrate (α-ketoglutarate) binding pockets. The calculations identify a persuccinate intermediate that triggers a bifurcation pathway in the enzyme and either react with a molecule of CO2 to form a carbonate or forms a high-valent iron(IV)-oxo species through heterolytic dioxygen bond cleavage. Our studies show that both the bifurcation pathways converge to the same intermediate again and can lead to ethylene products, although the two pathways have different kinetics. Interestingly, our studies also show that the iron(IV)-oxo itself can form a carbonate and ethylene but through much higher barriers. As a matter of fact, these barriers are higher in energy than the typical aliphatic hydroxylation barriers and may not be competitive with arginine hydroxylation. Inclusion of the l-arginine co-substrate into the model leads to minor changes in the structure and fold, but its charge and dipole moment does not seem to affect the first stage of the catalytic cycle. Moreover, the key activation barriers seem less affected by the inclusion of l-arginine into the model. We, therefore, believe that the role of l-arginine is to lock α-ketoglutarate and its products into a tight binding pocket to enable its degradation and to prevent early release of CO2. Our studies show that due to the distinct differences in α-ketoglutarate positioning between different arginine activating nonheme iron dioxygenases in the co-substrate binding pocket and its tighter binding in EFE, we predict that the release of CO2 is prevented in the first stage of the oxygen activation mechanism. This enables attack of CO2 on a persuccinate complex to form carbonate products, leading to ethylene formation. This work gives suggestions on the engineering of EFE into a hydroxylase or improving the ethylene biosynthesis.

Heterolytic Bond Cleavage in a Scissile Triarylmethane Mechanophore.

Covalent mechanophores display the cleavage of a weak covalent bond when a sufficiently high mechanical force is applied. Three different covalent bond breaking mechanisms have been documented thus far, including concerted, homolytic, and heterolytic scission. Motifs that display heterolytic cleavage typically separate according to non-scissile reaction pathways that afford zwitterions. Here, we report a new mechanochromic triarylmethane mechanophore, which dissociates according to a scissile heterolytic pathway and displays a pronounced mechanochromic response. The mechanophore was equipped with two styrenylic handles that allowed its incorporation as a cross-linker into poly(N,N-dimethylacrylamide) and poly(methyl acrylate-co-2-hydroxyethyl acrylate) networks. These materials are originally colorless, but compression or tensile deformation renders the materials colored. By combining tensile testing and in situ transmittance measurements, we show that this effect is related to scissile cleavage leading to colored triarylmethane carbocations.