Isomerization Route Research Articles

Flower-like hierarchical TS-1/Al2O3 composite supported NiMo catalysts for efficient hydrodesulfurization of dibenzothiophenes

Flower-like Al2O3 materials were successfully incorporated by TS-1 nanocrystals to synthesize Flower-like TS-1-Al2O3 (FTA) micro-mesoporous composite by a facile nano self-assembly method. FTA supported NiMo bimetallic catalysts (NiMo/FTA) were further constructed and applied to the hydrodesulfurization (HDS) reactions for dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT). FTA composites were constructed from flower-like pore structures stacked with nanosheets, which are conducive to the even load and dispersion of active species and the diffusion of macromolecular sulfur-containing compounds with relatively low resistance. The fabrication of TS-1 nanocrystals effectively enhanced the acidic sites, regulated the metal-support interaction, which could increase the stacking layer of MoS2 slabs, and producing more NiMoS-II type active phase. NiMo/FTA-10 presented the excellent HDS conversion of DBT (99.3 %) and 4,6-DMDBT (93.2 %) at 10 h−1, the highest reaction rate constant (2.6 × 10-7 mol g−1 s−1) and turnover frequency values (6.7 × 10-4 s−1) for 4,6-DMDBT HDS reaction. Compared to the direct desulfurization route (DDS), hydrogenation route (HYD) and isomerization route (ISO) can effectively eliminate the steric hindrance of 4,6-DMDBT, which is more conducive to the HDS reaction.

Effect of methyl substituent on adamantane pyrolysis at atmospheric and high pressure: A combined experimental and theoretical study

Adamantane derivatives, as promising high-density fuels, have been widely concerned in fields of volume-limited aerospace vehicles due to high density, heat of combustion and thermal oxidation stability. To reveal insights into their high-temperature decomposition behaviors, an experimental and theoretical investigation of adamantane (A) and 1-methyl adamantane (1-MA) pyrolysis was performed in a flow tube reactor at atmospheric to high pressure. Over twenty species were detected and identified, including C1-C5 light hydrocarbons, C5-C7 cyclic olefins as well as C6-C12 aromatics. The favorable decomposition channels of A and 1-MA are proposed and the effects of fuel structure characteristics and pressures on product formation behaviors are revealed. For the primary decomposition of A and 1-MA, the contributions of reaction types exhibit the obvious dependence on the pressures and temperatures, involving the unimolecular C-C dissociations by ring-opening, CH3-elimination as well as H-abstractions by H and CH3 attacking. Considering methyl-substitution weakens dissociation energies of C-C and C-H bonds and leads more H-abstraction sites, 1-MA shows a higher pyrolysis reactivity than A. The effects of structure characteristics are also embodied in the formation of newly chain-branched unsaturated species and the concentrations of common small hydrocarbons and aromatics. Compared to A decomposition, the methyl substituent in 1-MA promotes the emergence of 1-butene, 2-methyl-1-butene, mesitylene, methylindane and methylnaphthalene, and increases the concentrations of methane, 2-methylpropene and xylene isomers, formed via β-scission, hydrogen transfer, isomerization and dehydrogenation routes of fuel radicals. Meanwhile, more methyl-substitutions accelerate the decomposition of alkyl-adamantanes and pyrolysis activity follows by a sequence of dimethyl-adamantane > methyl-adamantane > adamantane, boosting the production of methyl-specific species.

Sustainable aviation fuel – Comprehensive study on highly selective isomerization route towards HEFA based bioadditives

This paper presents the results of a biofuel production process conducted using a cutting-edge, highly selective hydroisomerization catalyst. Rapeseed oil was used as a basic raw material for the synthesis of sustainable aviation fuel. The objective was to verify the catalysts hydroisomerization activity by comparison the effectiveness of obtained biofuel using a miniature jet engine and its compliance with current standards. The developed two-stage process by Łukasiewicz - ICSO involves the conversion of rapeseed oil into a C15–C18 hydrocarbon fraction through hydrodeoxygenation and subsequent hydroisomerization using the Pt/(SAPO-11 + Al2O3) catalyst. The overall average final yield of the aviation fuel fraction (C9–C18) after 500 h of testing was (60 ± 3)% based on the initial rapeseed oil used.In comparison to 100% petrochemical JET A-1 fraction, a BIO50 blend (mixture of biocomponent and JET A-1) is characterized by a more preferable crystallization temperature (−64 °C) and a 50% lower content of aromatic compounds fulfilling all the requirements of ASTM D-7566 standard. Additionally, tests conducted on a miniature jet engine have shown, that the BIO50 mixture has a higher calorific value compared to standard petrochemical fuel, what allows to reduce the overall fuel consumption and slightly lower CO2 and NOx emissions.

A novel route for isomerization of α-pinene oxide at room temperature under irradiation of light-emitting diodes

Present investigation demonstrates the potential use of HY-zeolite for photochemical applications in the selective isomerization of α-pinene oxide to carveol. In this study, ultraviolet lamp and LED (390 nm) light sources were employed under atmospheric conditions. The results revealed that light penetration through protonated zeolite cavity promotes the hydrogen radical formation, facilitating the isomerization reaction in the presence of dimethylacetamide solvent to achieve up to 60% and 40% conversion of α-pinene oxide to selective carveol (71%) under light irradiation. Here, using in situ spectroscopic studies (EPR and fluorescence), to confirm the hydrogen radical generation after light irradiation on the reaction mixture. Besides, the mechanistic pathway is proposed based on the experimental evidence of the formation of radicals, which is validated by the Density Functional Theory (DFT). By comparing electrical energy consumption for the same reaction using different reaction setups, it is understood that the energy requirement is nearly the same in the case of a reaction performed using a thermal reactor. The power consumption in reactions conducted using thermal, UV lamp and LED-based reactors was 1.6 kW/h, 1.5 kW/h, and 0.00144 kW/h, respectively. It is clear that the energy consumption in thermal and UV lamp-based reactors is higher than that of LED-based reactors, which was 1111 and 1041 times more than LED reactors respectively. Notably, the catalyst was found to be recyclable at least five consecutive runs, and the successful protocol was demonstrated up to 50 g scale.

Optimization of dendritic TS-1/Silica micro–mesoporous composites for efficient hydrodesulfurization of dibenzothiophene and 4,6-dimethyldibenzothiophene

A novel composite material (TD) composed of TS-1 microcrystalline and dendritic mesoporous silica nanospheres (DMSNs) was successfully prepared. The TD composite material had open pore structure and large specific surface area, which was conducive to the mass transfer of reactants and products. The Ti element in TS-1 could be used as an electron assistant, and the spillover d-electrons were conducive to the improvement of the sulfidation and dispersion of MoS2, thereby forming more type II MoS2 active phases. The incorporation of Ti could bring more Brønsted (B) and Lewis (L) acid, which was conducive to the hydrogenation pathway (HYD) selectivity (41.2%) of dibenzothiophene (DBT) hydrodesulfurization (HDS) and isomerization (ISO) route selectivity (21.9%) of 4,6-dimethyldibenzothiophene (4,6-DMDBT) HDS, thus improve the HDS activity of DBT and 4,6-DMDBT. NiMo/TD-70 (Aging temperature = 70 °C) had the best HDS activities of DBT (99.0%) and 4,6-DMDBT (93.7%) due to its large open pore structure, good acidity, suitable metal-support interaction (MSI) and perfect dispersion of the metallic active sites.

Ultralong room temperature phosphorescence and reversible mechanochromic luminescence in ionic crystals with structural isomerism

Photofunctional ionic crystals have become more and more appealing in the applications of light-emitting devices, optical imaging, and anti-counterfeiting. However, it is still limited to achieve ultralong room temperature phosphorescence (RTP) and stimuli-responsive property in ionic crystals due to the lack of valid design principles. Herein, we developed a new class of organic ionic crystals (sodium o-, m-, p-carboxyphenylborate, o-, m-, p-Nacpb) by a structural isomerization strategy, which could exhibit ultralong RTP and mechanochromic emission. Among the three isomers, m-Nacpb crystal exhibits the longest RTP lifetime up to 732.8 ms, which is ca. 120 times longer than that (6.1 ms) of o-Nacpb crystal. Interestingly, o-Nacpb could display mechano-responsive luminescence with tunable fluorescence-phosphorescence emissions and longer phosphorescence lifetime (increased by about 20-fold). Both experimental and theoretical studies indicate that the distinct RTP and mechanochromic luminescence properties of the organic ionic crystals are attributed to the alternation of molecular conformations and spatial packing modes. Moreover, potential applications including data encryption and decoration are demonstrated, benefiting from the varied phosphorescence lifetimes and good processability. Therefore, this work not only provides a rational isomerization route to prepare various organic ionic crystals with ultralong RTP and stimuli-responsive emission, but also supplies a facile way to develop the advanced information encryption applications.

Micro-mesoporous catalysts based on ZSM-5 zeolite synthesized from natural clay nanotubes: Preparation and application in the isomerization of C-8 aromatic fraction

Micro-mesoporous zeolite with ZSM-5 morphology was successfully synthesized by soft template and template-free methods using natural halloysite aluminosilicate nanotubes as a hard template and a source of aluminum and silicon. Formation of ZSM-5 crystal structure was confirmed by XRD. Textural properties and structural characteristics of functional materials, supports, and Pt-containing catalysts were examined by N2 physisorption, NH3-TPD, Py-FTIR, TEM, SEM, XRF techniques. Specific BET surface area of ZSM-5 zeolite prepared using TPABr as an organic template (ZSM-5(t):HNT) is 583 m2/g, whereas for the template-free counterpart (ZSM-5(tf):HNT) it reaches 225 m2/g. According to the Py-FTIR data, concentrations of Brønsted acid sites for ZSM-5(t):HNT and ZSM-5(tf):HNT are 295 and 93 μmol/g, whereas concentrations of Lewis acid sites are 79 and 41 μmol/g, respectively. Activity and selectivity of Pt catalysts based on the micro-mesoporous ZSM-5 zeolite-derived supports were evaluated in isomerization of C-8 aromatic fraction depending on the process conditions (temperature, feed space velocity). Because of the hierarchical micro-mesoporous structure, both catalysts provide xylenes transformation through the two isomerization routes (intra- and intermolecular). However, for the catalyst based on support synthesized through the template-free methods, the monomolecular reaction route is more preferable, and therefore the number of side reactions (disproportionation, transalkylation, and dealkylation) decreases.

Theoretical study of the cis–trans isomerization mechanism of azobenzene containing carboxy groups

DFT calculations were used to study the cis → trans isomerization mechanism of 4,4′-DCA and 3,3′-DCA. We have detected two inversion transition states TSInv1 and TSInv2 for 4,4′-DCA and 3,3′-DCA, respectively. Calculation results show that substituents of carboxy groups have no obvious effect on the coplanarity of benzene rings and NN bond for trans isomers. Potential energy surfaces were calculated for 4,4′-DCA and 3,3′-DCA. In the ground state, the rotation-assisted inversion pathway was found to be preferred. A conical intersection was found between the ground and first excited states along the rotation pathway, indicating that the rotation mechanism is favored in the first excited state. We also analyzed two possible isomerization routes through the inversion and rotation pathways of 4,4′-DCA and 3,3′-DCA of S2 states.

A study of the acidity on catalyst surface to control 1-butene reaction mechanism of metallosilicate catalysts

The metallosilicate catalysts (H-M-silicate, when M = Al, Fe, Cu, and Ni and Si/metal = 20) were synthesized and characterized by XRD, SEM-EDX, XRF, N2 adsorption and desorption, 27Al MAS NMR, XANES, EXAFS, NH3-TPD, NH3-IR, and TPO methods to investigate the effect of transition metals substitution in zeolite structure for 1-butene reaction. Only Fe3+ of H-Fe-silicate bonded in the MFI structure like H-ZSM-5, whereas transition metals of H-Cu-silicate and H-Ni-silicate embedded in zeolite matrix over catalyst surface; therefore: the reduction reaction occurred over metal of H-M-silicate catalyst during the reaction. There were two different roles of Brønsted acid site, detected by NH3-IR (B1 at ca. 1470 cm−1 and B2 at ca. 1660 cm−1). The B1 Brønsted acid site over micropore surface of catalyst (Si-OH-M) favored oligomerization-cracking route of 1-butene reaction, while butene isomerization route reacted on B2 Brønsted acid site (Si-OH) over external surface of catalyst (Acid strength: B1 > B2)

Hydrodesulfurization of dibenzothiophene and 4,6-dimethyldibenzothiophene over NiMo supported on yolk-shell silica catalysts with adjustable shell thickness and yolk size

Mesoporous yolk-shell silica spheres with different shell thicknesses and yolk sizes (YxSy) were synthesized by incubating mesostructured silica nanospheres with water. Al-modified YxSy-supported NiMo catalysts were prepared and applied to hydrodesulfurization (HDS) of dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT). The shell thickness and yolk size have a large effect on the HDS activities. Among the as-made catalysts, NiMo/Al-Y30S13 catalyst with relatively low shell thickness (13 nm), yolk size (30 nm) and proper structural stability exhibit the highest activities for HDS of DBT and 4,6-DMDBT at the weight time of 1.39–13.76 g min mol−1, of which its DBT conversion at 1.39 g min mol−1 (50.4%) is 1.5 times as that of the reference NiMo/Al2O3 (33.6%), four times as that of NiMo/Al-Y83S28 (12.3%) and what’s more, the HDS conversion of Al-Y30S13 could reach 99.5% at 13.76 g min mol−1 (about 2.5 ppm S remained). Its 4,6-DMDBT conversion at 1.39 g min mol−1 (27.1%) is almost 2 times as that over NiMo/Al2O3 (13.8%), and 2.7 times as that over NiMo/Al-Y83S28 (9.9%). Additionally, the 95.7% HDS conversion (about 16.6 ppm S remained) of Al-Y30S13 could be obtained at 13.76 g min mol−1. The good HDS performance of the NiMo/Al-Y30S13 catalyst could be derived from the synergistic effect of moderate shell thickness and relatively small yolk size, proper structural stability, appropriate acidity, moderate metal-support interaction (MSI), suitable dispersion and desirable stacking morphology of the Ni and Mo species. DBT HDS over the NiMo/Al-Y30S13 catalyst shows the lowest direct desulfurization (DDS)/hydrodesulfurization (HYD) ratio (2.70), demonstrating that the increase of HYD proportion could improve the ability of ultra-deep desulfurization of catalysts. 4,6-DMDBT HDS over the NiMo/Al-Y30S13 catalyst shows the highest selectivity of isomerization (ISO) route (69%), illustrating that the ISO route is the dominant pathway. Furthermore, the mechanisms of DBT and 4,6-DMDBT HDS are proposed over NiMo/Al-YxSy materials.

Facile synthesis of few-layer MoS2 nanosheets with different morphologies supported on Al-TUD-1 for efficient hydrodesulfurization of dibenzothiophene and 4,6-dimethyldibenzothiophene

Low-cost pure aluminum-based Al-TUD-1 mesoporous materials (AT) were successfully synthesized and the corresponding NiMo/AT catalysts were modified with Citric acid (CA), which were utilized for dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) hydrodesulfurization (HDS) reactions. CA could effectively modulate the acidity and metal-support-interaction (MSI) of NiMoCA(x)/AT catalysts, which were in favor of generating more MoS2 active species with higher sulfurization degree and higher dispersion degree. The morphology of the MoS2 active phase of NiMoCA(x)/AT catalysts was changed after the addition of CA. The NiMoCA(2)/AT catalyst showed the higher B/L ratio and higher S-edge/M-edge ratio, which was conducive to the isomerization (ISO) route selectivity (81%) of 4,6-DMDBT HDS, thus resulting the improvement of HDS activity of the NiMoCA(2)/AT catalyst. The NiMoCA(2)/AT exhibited the maximal DBT and 4,6-DMDBT HDS efficiency of 99.0% and 95.5% as well as maximal kHDS and TOF values of 4,6-DMDBT HDS (13.4 × 10−4 mol⋅g−1⋅h−1, 4.7 h−1) among other series NiMoCA(x)/AT catalysts and reference commercial NiMo/Al2O3 catalyst at the Weight hour space velocity (WHSV) of 10 h−1.

Impact of proximity between NiMoS and zeolitic HY sites on cyclohexene hydroconversion: An infrared operando study of sulfide catalysts

This work evaluates the effects of sulfide phase location on zeolite-containing catalysts in cyclohexene hydroconversion using the infrared operando technique. Parallels between activity, product yield, and surface species changes with time on stream and under pyridine poisoning were assessed on pure HY zeolite, sulfided NiMo/HY, NiMo/Al2O3, and NiMo/Al2O3 + HY. Isomerization activity could be related to zeolitic acidic OH groups and hydrogenation activity to sulfide phase sites. From the changes due to pyridine pulse injection, intrinsic activities could be calculated for isomerization (1-methyl-1-cyclopentene) and hydrogenation (cyclohexane) routes. The turnover frequency value for isomerization is greater than that for hydrogenation by one order of magnitude. Hence, the poisoning effect of one N-molecule on isomerization will be 10 times higher than that on the hydrogenation route. Whatever the location of the sulfide phase, the coke is mostly formed on the zeolite. As a consequence, on NiMo/HY, the close proximity between acidic and sulfide sites results in lower formation of hydrogenated products, due to blockage of some sulfide sites by coke. In contrast, the hydrogenation activity of NiMo/Al2O3 + HY is less affected by coke, NiMoS being mostly located on alumina. However, the results show that the close proximity between acid and sulfide sites allows a higher degree of hydrogenation of the isomerization product (1-methyl-1-cyclopentene). Thus, the higher proximity has a beneficial effect on methylcyclopentane formation.

The oxidation mechanism of gas-phase ozonolysis of limonene in the atmosphere.

Limonene with endo- and exo-double bonds is a significant monoterpene in the atmosphere and has high reactivity towards O3. We investigated the atmospheric oxidation mechanism of limonene ozonolysis using a high level quantum chemistry calculation coupled with RRKM-ME kinetic simulation. The additions of O3 can take place at both the endo- and exo-double bonds with a branching ratio of 0.87 : 0.13, forming four major highly energized CIs* (named Syn-2a*, Syn-2b*, Anti-2b* and Anti-2c*) with the relative higher fractions of 0.21 : 0.35 : 0.27 : 0.11. A yield of 4% for Limona-ketone was obtained as well. For the unimolecular isomerization pathways of limonene + O3 → POZs → CIs* → SOZ, VHP, or dioxirane, five, one, or none of the internal rotations are treated as hindered internal rotors for CIs*. We obtained percentages of 0.59 : 0.18 : 0.14 in total for separate isomerization routes in the formation of VHPs, dioxirane and SOZs from CIs* using the fourth-order Runge-Kutta method. Additionally, a yield of ∼5% was acquired for stabilized CIs compiling the fractions of different addition routes. About ∼10% of stabilized Anti-2b would isomerize to VHP and 90% would isomerize to SOZs. Isomerization to VHPs dominates the fate of stabilized Syn-2a, Syn-2b and Anti-2c. The overall yield of OH radicals was 0.61. Our study suggested a yield of 0.17 for stabilized SOZs and 0.18 for dioxirane, although both their fates are ambiguous.

Structural Screening and Design of Dendritic Micro-Mesoporous Composites for Efficient Hydrodesulfurization of Dibenzothiophene and 4,6-Dimethyldibenzothiophene.

Novel dendritic micro-mesoporous TS-1/dendritic mesoporous silica nanoparticle (DMSN) composites (TD) were assembled by TS-1 nanocrystals with ultrasmall particle size and strong acidity. TS-1 seeds and DMSNs were composited via the Ti-O-Si chemical bond, which stimulate the generation of Brønsted (B) and Lewis (L) acids. The spillover d-electrons produced by the Ti element of TS-1 seeds produced a spillover of d-electrons, which could interact with the surface of MoS2 phases, thereby reducing Mo-S interactions and create sulfur vacancies that are favorable for dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) hydrodesulfurization (HDS) reactions. The increased amount of B&L acid of NiMo/TD-2.0 with cetyltrimethylammonium bromide/sodium salicylate molar ratio of 2.0 played an important role in facilitating the hydrogenation (HYD) route of DBT HDS and the isomerization (ISO) route of 4,6-DMDBT HDS, which is more favorable for the reduction of steric hindrance of DBT and 4,6-DMDBT reactants in the HDS reaction process. The NiMo/TD-2.0 catalyst exhibited the highest turnover frequency (TOF) value and HDS reaction rate constant (kHDS) of DBT and 4,6-DMDBT due to its ultrasmall particle size, uniform spherical dendritic morphology, strong B&L acidity, and good stacking degree.

Exploring isomerization dynamics on a potential energy surface with an index-2 saddle using lagrangian descriptors

In this paper we explore the phase space structures governing isomerization dynamics on a potential energy surface with four wells and an index-2 saddle. For this model, we analyze the influence that coupling both degrees of freedom of the system and breaking the symmetry of the problem have on the geometrical template of phase space structures that characterizes reaction. To achieve this goal we apply the method of Lagrangian descriptors, a technique with the capability of unveiling the key invariant manifolds that determine transport processes in nonlinear dynamical systems. This approach reveals with extraordinary detail the intricate geometry of the isomerization routes interconnecting the different potential wells, and provides us with valuable information to distinguish between initial conditions that undergo sequential and concerted isomerization.

Unveiling New Isomers and Rearrangement Routes on the C7H8+ Potential Energy Surface

The unimolecular reactions of C7H8+ radical cations are among those most studied by mass spectrometry, especially the rearrangement of toluene and cycloheptatriene molecular ions, which are directly connected to the formation of benzylium and tropylium cations. This study reveals important new isomers and isomerization pathways on the C7H8+ potential energy surface, through the application of gas-phase electronic photodissociation spectroscopy in conjunction with ab initio calculations. Presented are the first gas-phase vibrationally resolved electronic spectra of the o-isotoluene, norcaradiene, bicyclo[3.2.0]hepta-2,6-diene radical cations, and ring-opened products from cyclic C7H8+ species. The isomerization route from the norbornadiene radical cation to the toluene radical cation, which competes with isomerization to the bicyclo[2.2.1]hepta-2-ene-5-yl-7-ylium radical cation, is identified. Further, this work expands understanding of the C7H8+ potential energy surface by connecting spiro[2.4]hepta-4,6-diene and acyclic 1,2,4,6-heptatetraene radical cations, and confirms the important role of the o-isotoluene radical cation in the interconversion pathways of C7H8+ species.

Sigma- versus Pi-Dimerization Modes of Triangulene.

We show that the diradicaloid triangulene, a graphene nano-flake molecule, can aggregate in a variety of dimerization modes. We found by density functional theory modeling a number of triangulene dimers including six doubly bonded σ-dimers in addition to the previously reported six pancake bonded π-dimer isomers. The σ-dimers display a wide range of stabilities: the interaction energy of the most stable σ-dimer is -25.17 kcal mol-1 . Besides the doubly bonded σ-dimers with closed shell ground states, we also found an open-shell singly σ-bonded diradicaloid dimer. We found an interesting isomerization route between a doubly bonded σ-dimer, a singly bonded σ-dimer with a low-lying triplet state and two π-bonded dimers with low-lying quintet states. Derivatives of triangulene, trioxo-triangulenes (TOTs) have been previously characterized experimentally. Here, we show the reasons why so far only the π-dimer but not the σ-dimer was experimentally observed for all TOTs.

STUDY OF THE CATALYTIC CONVERSION AND ADSORPTION OF ABIETIC ACID ON ACTIVATED CARBON: EFFECT OF SURFACE ACIDITY

This study reports the adsorption and catalytic conversion of abietic acid as representative compound of tall oil, using activated carbons. Acid functional groups present on CGRAN activated carbons favored the adsorption of abietic acid, probably through a physical adsorption mechanism. In contrast, the conversion of abietic acid was not favored in DARCO activated carbon by increase of acid sites thought HNO3 treatment. The detection of neoabietic, palustric and/or levopimaric acids as reaction products indicate that the transformation of abietic acid was by dehydrogenation and/or isomerization routes. The negative influence of acid sites on the catalytic activity, in addition to the non-detection of volatile products, suggests that the cracking pathway for the conversion of abietic acid over these catalysts can be ruled out. Contrasting effects of the surface groups on the adsorption capacity and the conversion was observed: strong acid sites of CGRAN activated carbon favor the adsorption of abietic acid and decrease competitive adsorption between substrate and solvent, while conversion is not favored by these acid sites.

Acid strength and metal-acid proximity effects on methylcyclohexane ring contraction turnover rates and selectivities

Methylcyclohexane ring contraction is used here to assess the effects of acid strength and metal-acid site proximity on turnover rates and selectivities for bifunctional catalysts consisting of Keggin type polyoxometalates (POM) with different central atoms that act as Brønsted acids. Bifunctional catalysts with metal sites that fully equilibrate cycloalkanes and cycloalkenes give methylcyclohexene conversion rate constants that decreased exponentially with increasing deprotonation energy, a rigorous descriptor of acid strength, consistent with the ion-pair character of transition states that mediate the kinetically-relevant ring contraction of bound methylcyclohexoxide intermediates. The measured rates of formation of each alkylcyclopentane isomer, however, do not reflect their intrinsic formation kinetics, because of fast diffusion-enhanced interconversions within acid domains; thus, isomer selectivities cannot be used to infer, even indirectly, the strength of acid sites, as often proposed in previous studies. Selectivities reflect instead diffusional effects that become more severe as the number and strength of acid sites and the size and diffusive resistances increase within these acid domains, which shift, in turn, the products formed from relative abundances dictated by kinetics to those prescribed by thermodynamics. A rigorous accounting of these diffusional effects using a kinetic-transport model leads to ratios of intrinsic rate constants for the formation of the different alkylcyclopentane isomers that do not depend on acid strength, because all isomerization routes are mediated by bicyclo[3.1.0]hexyl cation transition states similar in the amount and location of charge and that therefore benefit to the same extent from the more stable conjugate anions characteristic of stronger acids.

Reactivity, vibrational spectroscopy, internal rotation and thermochemical aspects of methylarsine

The aim of this investigation was to perform a characterization of the spectroscopic and thermodynamic properties of methylarsine (CH3AsH2). Post-Hartree-Fock, 29 DFT methods and eight different composite methodologies were employed in these analyses. A comparison between harmonic and anharmonic frequency accuracies in reproducing the observable frequencies was performed here. In addition, the CH3AsH2→CH2AsH3 isomerization barrier energy was estimated in 100kcalmol−1, whereas the H2-release routes barrier heights were in the 45–107kcalmol−1 range. A rate constant of 10−66s−1 was predicted regarding the isomerization route, while the CH2AsH3 hydrogen elimination mechanism is faster than the methylarsine one. The transition state structure of the CH3AsH2 internal rotational barrier energy varied between 1.0 and 1.4kcalmol−1. For the CH2AsH3 internal rotation the estimated barrier heights varied 0.6–2.5kcalmol−1. The adiabatic ionization energy and the heat of formation each structure was also calculated here.