A predictive model for unimolecular reactions: Reactions of unsaturated carbonium ions

The major slow unimolecular reactions undergone by C₄H₇⁺, C₅H₉⁺ and C₆H⁺₁₁ are discussed in terms of a potential surface approach and the organic chemist's concept of mechanism. It is shown that the observed decompositions which do not involve σ-bond formation in the dissociation step are precisely those expected from the model. Further use of the model correctly predicts the slow reactions of C₇H⁺₁₃ which have not previously been reported. The approach also permits useful limits to be set on the transition state energies for reactions involving σ-bond formation in the dissociation step (H₂,CH₄ loss). It is concluded that stepwise addition of ethylene to the allyl cation is preferred to a concerted 4-electron process which is symmetry forbidden.     

Mechanism‐Based Condition Screening for Sustainable Catalysis in Single‐Electron Steps by Cyclic Voltammetry

A cyclic‐voltammetry‐based screening method for Cp₂TiX‐catalyzed reactions is introduced. Our mechanism‐based approach enables the study of the influence of various additives on the electrochemically generated active catalyst Cp₂TiX, which is in equilibrium with catalytically inactive [Cp₂TiX₂]^?. Thioureas and ureas are most efficient in the generation of Cp₂TiX in THF. Knowing the precise position of the equilibrium between Cp₂TiX and [Cp₂TiX₂]^? allowed us to identify reaction conditions for the bulk electrolysis of Cp₂TiX₂ complexes and for Cp₂TiX‐catayzed radical arylations without having to carry out the reactions. Our time‐ and resource‐efficient approach is of general interest for the design of catalytic reactions that proceed in single‐electron steps.     

Solid state decompositions: the interpretation of kinetic and microscopic data and the formulation of a reaction mechanism

This article discusses current theoretical concepts that relate to the role of interfaces in reactions involving solids. It is emphasized that the isothermal kinetic characteristics of such reactions are often determined by the progressive changes of interface geometry as reaction advances, and that obedience to a particular rate equation does not necessarily provide information concerning the chemistry of the processes involved. Evidence concerning reactant and product textures and the conditions prevailing at an interface can, in suitable systems, be deduced from microscopic examination of the reactant-product contact zone. Observations of this type have been used to develop a classification scheme for nucleus functions in various reactions. The value of this general approach, the separate and complementary consideration of reaction geometry and interface chemistry in formulating reaction mechanisms, is discussed with reference to the following rate processes: alum dehydrations, the reaction KBr+Cl₂ → KCl+BrCl, the decompositions of (NH₄)₂Cr₂O₇, copper malonate, and other metal carboxylates. It is concluded that modern methods of microscopic examination afford a direct and powerful technique for the characterization of the interfacial chemical changes that occur during reactions of solids.     

Use of ion-molecule reaction equilibria to identify structural isomers

A new approach is described for identifying structural isomers which cannot be distin-guished on the basis of their electron-impact mass spectra. Using a pulsed ion cyclotron resonance mass spectrometer, equilibrium constsnts are measured for ion-molecule reactions involving various C₈H₁₀ isomers and C₇H₈O isomers. The equilibrium constants are shown to be highly sensitive to the structural features of the various isomers.     

Silica-Supported MnII Sites as Efficient Catalysts for Carbonyl Hydroboration,Hydrosilylation, and Transesterification

Manganese, the third most abundant transition-metal element after iron and titanium, has recently been demonstrated to be an effective homogeneous catalyst in numerous reactions. Herein, the preparation of silica-supported Mn^II sites is reported using Surface Organometallic Chemistry (SOMC), combined with tailored thermolytic molecular precursors approach based on Mn₂[OSi(OtBu)₃]₄ and Mn{N(SiMe₃)₂}₂⋅THF. These supported Mn^II sites, free of organic ligands, efficiently catalyze numerous reactions: hydroboration and hydrosilylation of ketones and aldehydes as well as the transesterification of industrially relevant substrates.     

On the use of localized orbitals and restricted alternant orbitals in chemical systems

An analysis of the transformation of localized orbitals into restricted alternant orbitals is proposed. This approach has the advantage of expressing the wave-function in an orbital product while some electron correlation is introduced permitting the study of dissociation reactions. All applications of the orbital technique may be made as easily as with RHF, but with the additional possibility of studying chemical radicals. Some illustrations of this fact are shown for the molecules HF, H₂O, NH₃, CH₄, C₂H₆ and for the dissociation reactions of CH₄ and C₂H₆ generating CH₃ radicals.     

Multiply Confined Nickel Nanocatalysts Produced by Atomic Layer Deposition for Hydrogenation Reactions

To design highly efficient catalysts, new concepts for optimizing the metal–support interactions are desirable. Here we introduce a facile and general template approach assisted by atomic layer deposition (ALD), to fabricate a multiply confined Ni‐based nanocatalyst. The Ni nanoparticles are not only confined in Al₂O₃ nanotubes, but also embedded in the cavities of Al₂O₃ interior wall. The cavities create more Ni–Al₂O₃ interfacial sites, which facilitate hydrogenation reactions. The nanotubes inhibit the leaching and detachment of Ni nanoparticles. Compared with the Ni‐based catalyst supported on the outer surface of Al₂O₃ nanotubes, the multiply confined catalyst shows a striking improvement of catalytic activity and stability in hydrogenation reactions. Our ALD‐assisted template method is general and can be extended for other multiply confined nanoreactors, which may have potential applications in many heterogeneous reactions.     

Force in SCF theories. MC SCF and open-shell RHF theories

A theorem reported for Hartree-Fock SCF theory is shown to be valid for general MC SCF and open-shell RHF theories - a sufficient condition for these wavefunctions to satisfy the Hellmann-Feynman theorem is that the basis set includes the derivative AO ^?X_r/^?X_rfor any basis X_r. The new force approach is applicable to wider fields including electronic processes in chemical reactions. Test calculations are given for some simple systems.     

Cavity-Directed Synthesis of Labile Polyoxometalates for Catalysis in Confined Spaces

The artificial microenvironments inside coordination cages have gained significant attention for performing enzyme-like catalytic reactions by facilitating the formation of labile and complex molecules through a “ship-in-a-bottle” approach. Despite many fascinating examples, this approach remains scarcely explored in the context of synthesizing metallic clusters such as polyoxometalates (POMs). The development of innovative approaches to control and influence the speciation of POMs in aqueous solutions would greatly advance their applicability and could ultimately lead to the formation of elusive clusters that cannot be synthesized by using traditional methods. In this study, we employ host–guest stabilization within a coordination cage to enable a novel cavity-directed synthesis of labile POMs in aqueous solutions under mild conditions. The elusive Lindqvist [M₆O₁₉]²⁻ (M=Mo or W) POMs were successfully synthesized at room temperature via the condensation of molybdate or tungstate building blocks within the confined cavity of a robust and water-soluble Pt₆L₄(NO₃)₁₂ coordination cage. Importantly, the encapsulation of these POMs enhances their stability in water, rendering them efficient catalysts for environmentally friendly and selective sulfoxidation reactions using H₂O₂ as a green oxidant in a pure aqueous medium. The approach developed in this paper offers a means to synthesize and stabilize the otherwise unstable metal-oxo clusters in water, which can broaden the scope of their applications.     

Photoinduced electron transfer and interfacial photocatalysis behaviour of ZnS/CdS binary co-colloid system

The interfacial photoinduced electron transfer and related secondary photochemical behaviour in the system of ZnS/CdS co-colloid superfine particles were studied by means of ESR and fluorescence spectroscopy techniques. The photoinduced charge-separation and the radical intermediates produced in the secondary redox reactions initiated via charge separation, as well as the mechanism of reaction processes, were investigated in detail through simultaneous excitation of two colloid components or only one of them. Research results indicated that, as E_(g(ZnS))>E_λ>E_(g(CdS)), only CdS in co-colloid system might be excited. The transfer process of electron from the conduction band of CdS to the conduction band of ZnS is forbidden, and under the excitation wavelength range used, the electron transfer of cocolloid system was impossible, thus the photo redox reactions of the substrate in co-colloid system had no obvious difference from those reactions happening in single colloid system. While the excitation wav     

Catalytic oxidation of hydrogen on platinum

Using the thermochemical approach to interpret the kinetics of heterogeneous reactions and the mechanism of congruent dissociative decomposition of solids developed in the 1980s and (re)analyzing the experimental data available in the literature over the last 90 years, a novel mechanism for the catalytic oxidation of H₂ by PtO₂ is proposed. In place of the conventional Langmuir–Hinshelwood and Eley–Rideal adsorption reaction mechanisms, our model is based on the reactions: PtO₂(s) + 2H₂ ? Pt(g) + 2H₂O and Pt(g) + O₂ ? PtO₂(g) → PtO₂(s). The first reaction determines the kinetics of H₂ oxidation and the second determines the kinetics of restoration of the PtO₂ layer. Thermochemical consideration of kinetic features of this model enables (for first time in the history of this reaction) the enthalpy and equilibrium constants for H₂ oxidation on platinum to be calculated. The results are in good agreement with experimental data. In addition, the proposed mechanism explains the origin of the surface-retexturing effect, the impact of autocatalysis, the influence of H₂O vapor on oxidation rate, and the three-fold variation of the Arrhenius E parameter with temperature. This all convincingly demonstrates the value of the thermochemical approach in interpreting heterogeneous reactions.     

Steric Effects in Nucleophilic Aromatic Substitution reactions with aromatic amines 12th communication on nucleophilic aromatic substitution reactions

The kinetics of the S_NAr reactions of aniline and N-methylaniline with a variety of substituted nitrochlorobenzenes in acetonitrile demonstrate that the formation of the intermediate σ-complex is rate determining. The ratio of the rate constants of the aniline and the N-methylaniline reactions (k_A/k_M) increases with increasing size of the 6-substituent; with picryl chloride k_A/k_M reaches a value of over 20 000. The reaction of aniline with 4-X-2,6-dinitrochlorobenzenes is subject to considerably larger para-substituent effects than the corresponding reactions with N-methylaniline. These results are interpreted in terms of two effects: (i) A primary steric effect, which renders the approach of N-methylaniline to the substrate difficult. (ii) A shift towards earlier, more reactant-like transition state structures caused by the primary steric effect. In early transition states the activating power of the electron-withdrawing substituents in the substrate is expected to be relatively small. An early transition state for the slow N-methylaniline reaction and a late transition state for the fast aniline reaction is in apparent contradiction to what would be expected on the basis of the Hammond postulate.     

Cycloaddition Reactions and Dendritic Polymer Architectures – A Perfect Match

Summery: The potential of cycloaddition (CA) reactions for the synthesis of dendritic polymers is pointed out. The [4 + 2] Diels Alder cycloaddition as well as 1,3-dipolar CA reactions including “click chemistry” are addressed, and the advantages of these reactions like high selectivity, thus high tolerance towards additional functionalities, high yields and synthesis under mild reaction conditions are highlighted. New perfectly branched dendrimers as well as hyperbranched polymers have been prepared and modified using the 1,3-dipolar cycloaddition reaction of azines with alkynes. The 1,3-dipolar CA reaction of bisazine with maleimides results in hyperbranched and thus, irregular and broadly distributed polymers though with a degree of branching of 100% due to special intermediate formation. The [4 + 2] Diels Alder cycloaddition was successfully applied for the synthesis of highly branched polyphenylene structures using the AB₂ + AB and the A₂ + B₃ approach. CA reactions are also very suitable for highly efficient polymer analogous reactions and thus, they can also be used to prepare complex polymer architectures like dendronized polymers.     

Top‐Down and Bottom‐Up Approaches in Engineering 1 T Phase Molybdenum Disulfide (MoS2): Towards Highly Catalytically Active Materials

The metallic 1 T phase of MoS₂ has been widely identified to be responsible for the improved performances of MoS₂ in applications including hydrogen evolution reactions and electrochemical supercapacitors. To this aim, various synthetic methods have been reported to obtain 1 T phase‐rich MoS₂. Here, the aim is to evaluate the efficiencies of the bottom‐up (hydrothermal reaction) and top‐down (chemical exfoliation) approaches in producing 1 T phase MoS₂. It is established in this study that the 1 T phase MoS₂ produced through the bottom‐up approach contains a high proportion of 1 T phase and demonstrates excellent electrochemical and electrical properties. Its performance in the hydrogen evolution reaction and electrochemical supercapacitors also surpassed that of 1 T phase MoS₂ produced through a top‐down approach.     

Fast CO<Subscript>2</Subscript> sequestration by aerogel composites

The increasingly evident impact of anthropogenic CO₂ emissions on climate change and associated environmental effects is stimulating the search for viable methods to remove this gas. One of the most promising strategies is the long-term storage of CO₂ in inert, insoluble and thermodynamically-stable materials. This strategy mimics the natural reactions that transform silicates into carbonates regulating the cycle of CO₂ on the surface of the Earth, operating on a geological time-scale. Consequently, the aim is to accelerate these reactions to be applicable on the timescale of human lives. We present the various technologies developed or proposed to date, based on this particular approach. The principal limiting factor is that high pressures and temperatures are required to produce appropriate materials capable of CO₂ sequestration and storage. Nevertheless, the synthetic materials known as aerogels can be modified in shape, size and chemical functionality so as to catalyse the process of CO₂ elimination through silicates (of Ca or Mg), considerably reducing the reaction time and working at atmospheric pressure and temperature.     

Bimolecular QRRK analysis of methyl radical reactions

Reactions which proceed through energized adducts, including radical recombinations, insertions, and addition to unsaturates, frequently exhibit unusual kinetic behavior. The branching ratios among various product channels are often complex functions of both temperature and pressure. Four such reactions involving methyl radicals are analyzed by combining chemical activation distribution functions with QRRK methods to predict rate constants for each channel. These include three oxidation paths, CH₃ + O, CH₃ + O₂, CH₃ + OH, and the addition reaction CH₃ + C₂H₂. These predictions are compared to experiments wherever possible; generally, the agreement is quite satisfactory. Analysis of the energetics of the various reaction channels, using parameters which are readily available, provides a convenient framework for prediction. Suggested rate constants for the various channels for the four reactions are given at three pressures, 20, 760, and 7600 Torr, for the temperature range 300–2500 K. The approach used here can easily be applied to other reactions.     

Semiempirical MO calculations on symmetry governed reactions

Two symmetry governed reactions, the electrocyclic transformation of planar cyclopropyl cation to allyl cation and the dimerization of ethylene to cyclobutane, are examined using a modified INDO method. Results for the cyclopropyl-allyl cation reaction agree well with previously publishedab initio results, and are much improved over previously published CNDO results. The symmetry-allowed disrotatory path is predicted to be significantly favored over the forbidden conrotatory transition. For the ethylene-cyclobutane system two surprising results are predicted within the constraints imposed upon the reaction path: first, that the entire reaction should occur within a small range in the separation of the two ethylene molecules as they approach one another, and second, that the symmetry-forbidden [2 _s +2 _s addition should be slightly favored over the symmetry-allowed [2 _s +2 _a addition. Since the Woodward-Hoffmann rules deal exclusively with changes in electronic energy, it is suggested that they should be applied with some caution to reactions in which changes in nuclear repulsion are quite large during the reaction process.     

Ab initio studies of chemical equilibria. Equilibria containing first row hydrides AH2, AH3, and AH4 and their positive ions

Equilibrium constants were calculated for fourteen simple reactions involving AH₂, AH₃, and AH₄ first row hydrides and their positive ions. Except for the “experimental” correlation energies used, the theoretical approach is entirely non-empirical in character. The results suggest that if the correlation effects were accounted for in a more sophisticated way, most of the calculated equilibrium constants would be more reliable than the available experimental data.