Intramolecular Catalytic Hydrogen Atom Transfer (CHAT).

Intramolecular catalysis (IntraCat) is the acceleration of a process at one site of a molecule catalyzed by a functional group in the same molecule; an external agent such as a solvent typically facilitates it. Here, we report a general first-principles-based IntraCat mechanism, which strictly occurs within a single molecule with no coreagent being involved─we call it intramolecular catalytic transfer of hydrogen atoms (CHAT). A reactive part of a molecule (chat catalyst moiety or chat agent, represented by -OOH, -COOH, -SH, -CH2OH, -HPO4, or another bifunctional H-donor/acceptor group) catalyzes an interconversion process, such as keto-enol or amino-imino tautomerization, and cyclization in the same molecule, while being regenerated in the process. It can thus be regarded as an intramolecular version of the intermolecular H atom transfer processes mediated by an external molecular catalyst, e.g., dihydrogen, water, or a carboxylic acid. Earlier, we proposed a general mechanistic systematization of intermolecular processes, illustrated in the simplest case of the H2-mediated reactions classified as dihydrogen catalysis [Asatryan, R.; et al. Catal. Rev.: Sci. Eng., 2014, 56, 403-475]. Following this systematization, the CHAT catalysis belongs to the category of relay transfer of H atoms, albeit in an intramolecular manner. A broader class of intramolecular processes includes all types of H-transfer reactions stimulated by an H-migration, which we call self-catalyzed H atom transfer (SC-HAT). The CHAT mechanism comprises a subset of SC-HAT in which the catalytic moiety is regenerated (i.e., acts as a true catalyst and not a reagent). We provide several characteristic examples of CHAT mechanism based on detailed analysis of the corresponding potential energy surfaces. All such cases showed a dramatically reduced activation barrier relative to the corresponding uncatalyzed H-transfer reactions. For example, we show that CHAT can facilitate long-range H-migration in larger molecules and can occur multiple times in one molecule with multiple interconverting groups. It also facilitates amino-imino tautomerization of unsaturated GABA-analogues and peptides, as well as intramolecular cyclization processes to form heterocycles, e.g., oxygenated rings. CHAT pathways may also explain the pH-dependent increase of mutarotation rate of glucose-6-phosphate demonstrated in pioneering experiments that introduced the classical IntraCat concept. In addition, we identify a ground electronic state CHAT pathway as an alternative to the UV-promoted long-range molecular crane keto-enol conversion with a remarkably low activation energy. To initially assess the possible impact of the new keto-enol conversion pathway on combustion of n-alkanes, we present a detailed kinetic analysis of isomerization and decomposition of pentane-2,4-ketohydroperoxide (2,4-KHP). The results are compared with key alternative reactions, including direct dissociation and Korcek channels (for which a new alkyl group migration channel is also identified), revealing the competitiveness of the CHAT pathway across a range of conditions. Taken together, this work provides insight into a general class of reaction pathways that has not previously being systematically considered and that may occur in a broad range of contexts from combustion to atmospheric chemistry to biochemistry.

Automated Generation of a Compact Chemical Kinetic Model for n-Pentane Combustion.

We have employed automated mechanism generation tools to construct a detailed chemical kinetic model for combustion of n-pentane, as a step toward the generation of compact kinetic models for larger alkanes. Pentane is of particular interest as a prototype for combustion of alkanes and as the smallest paraffin employed as a hybrid rocket fuel, albeit at cryogenic conditions. A reaction mechanism for pentane combustion thus provides a foundation for modeling combustion of extra-large alkanes (paraffins) that are of more practical interest as hybrid rocket fuels, for which manual construction becomes infeasible. Here, an n-pentane combustion kinetic model is developed using the open-source software package Reaction Mechanism Generator (RMG). The model was generated and tested across a range of temperatures (650 to 1350 K) and equivalence ratios (0.5, 1.0, 2.0) at pressures of 1 and 10 atm. Available thermodynamic and kinetic databases were incorporated wherever possible. Predictions using the mechanism were validated against the published laminar burning velocities (Su) and ignition delay times (IDT) of n-pentane. To improve the model performance, a comprehensive analysis, including reaction path and sensitivity analyses of n-pentane oxidation, was performed, leading us to modify the thermochemistry and rate parameters for a few key species and reactions. These were combined as a separate data set, an RMG library, that was then used during mechanism generation. The resulting model predicted IDTs as accurately as the best manually constructed mechanisms, while remaining much more compact. It predicted flame speeds to within 10% of published experimental results. The degree of success of automated mechanism generation for this case suggests that it can be extended to construct reliable and compact models for combustion of larger n-alkanes, particularly when using this mechanism as a seed submodel.

Metal-Free Biomass-Derived Environmentally Persistent Free Radicals (Bio-EPFRs) from Lignin Pyrolysis.

To assess contribution of the radicals formed from biomass burning, our recent findings toward the formation of resonantly stabilized persistent radicals from hydrolytic lignin pyrolysis in a metal-free environment are presented in detail. Such radicals have particularly been identified during fast pyrolysis of lignin dispersed into the gas phase in a flow reactor. The trapped radicals were analyzed by X-band electron paramagnetic resonance (EPR) and high-frequency (HF) EPR spectroscopy. To conceptualize available data, the metal-free biogenic bulky stable radicals with extended conjugated backbones are suggested to categorize as a new type of metal-free environmentally persistent free radicals (EPFRs) (bio-EPFRs). They can be originated not only from lignin/biomass pyrolysis but also during various thermal processes in combustion reactors and media, including tobacco smoke, anthropogenic sources and wildfires (forest/bushfires), and so on. The persistency of bio-EPFRs from lignin gas-phase pyrolysis was outlined with the evaluated lifetime of two groups of radicals being 33 and 143 h, respectively. The experimental results from pyrolysis of coniferyl alcohol as a model compound of lignin in the same fast flow reactor, along with our detailed potential energy surface analyses using high-level DFT and ab initio methods toward decomposition of a few other model compounds reported earlier, provide a mechanistic view on the formation of C- and O-centered radicals during lignin gas-phase pyrolysis. The preliminary measurements using HF-EPR spectroscopy also support the existence of O-centered radicals in the radical mixtures from pyrolysis of lignin possessing a high g value (2.0048).

OH-Initiated Reactions of para-Coumaryl Alcohol Relevant to the Lignin Pyrolysis. Part III. Kinetics of H-Abstraction by H, OH, and CH3 Radicals.

Lignin is the most complex component of biomass, and development of a detailed chemical kinetic model for biomass pyrolysis mainly relies on the understanding of the lignin decomposition kinetics. para-Coumaryl alcohol (p-CMA, HOPh-CH═CH-CH2OH), the focus of our analysis, is the simplest of the lignin monomers (monolignols) containing a typical side-chain double bond and both alkyl- and phenolic-type OH-groups. In parts I and II of our work (Asatryan, R. J. Phys. Chem. A 2019, 123, 2570-2585; Hudzik, J. M. J. Phys. Chem. A 2020, current issue), we created a detailed potential energy surface (PES) and performed a kinetic analysis of chemically activated, unimolecular, and bimolecular reactions pathways for p-CMA + OH. Reaction pathways analyzed include dissociation, intramolecular abstraction, group transfer, and elimination processes. The α- and ß-carbon addition reactions generate 1,3- (RA1) and 1,2-diol (RB1) adduct radicals, respectively. Well depths are approximately 29 and 41 kcal/mol below the p-CMA + OH entrance level. Kinetic analysis aides in determining the major pathways for our conventional and fractional pyrolysis experiments. The current paper focuses on the H-abstraction reactions via H, OH, and CH3 light ("pool") radicals from p-CMA. The thermochemical properties of all stable, radical, and transition-state species were determined using the ωB97XD density functional theory (DFT) and higher-level CBS-QB3 composite methods. Barrier heights from the prereaction complexes, for OH-radical abstractions, to the transition states for the propanoid side chain are compared to the model H-abstraction reactions of allyl alcohol (AA) with OH and p-CMA with H and CH3 radicals. The lowest-energy, most stable, p-CMA radical formed is at the C9 allylic position (p-CMA-C9j) with exothermicity of 26.63, 41.32, and 27.34 kcal/mol for H, OH, and CH3, respectively. For OH-radical abstraction at this position, our findings are consistent with corresponding data on AA + OH at 37.44 kcal/mol and similar to that of RB1. A similar stable radical with an exothermicity of 34.95 kcal/mol occurs for the phenol hydroxyl group, generating the p-CMA-O4j radical. H-abstraction pathways are considered in relation to other major pathways previously considered for p-CMA + OH reactions including H-atom shifts, dehydration, and ß-scission reactions. Derived rate coefficients for substituted phenols can be utilized in detailed kinetic models for lignin/biomass pyrolysis.

OH-Initiated Reactions of para-Coumaryl Alcohol Relevant to the Lignin Pyrolysis. Part II. Kinetic Analysis.

Monolignols are precursor units and primary products of lignin pyrolysis. The currently available global (lumped) and semidetailed kinetic models, however, are lacking the comprehensive decomposition kinetics of these key intermediates in order to advance toward the fundamentally based detailed chemical-kinetic models of biomass pyrolysis. para-Coumaryl alcohol (HOPh-CH═CH-CH2OH, p-CMA) is the simplest of the three basic monolignols containing a typical side-chain double bond and both alkyl and phenolic type OH groups. The two other monomers additionally contain one and two methoxy groups, respectively, attached to the benzene ring. Previously, we developed a detailed fundamentally based mechanism for unimolecular decomposition of p-CMA (as well as its truncated allyl and cinnamyl alcohol models) and explored its reactivity toward H radicals generated during pyrolysis. The reactions of p-CMA with pyrolytic OH radicals is another set of key reactions particularly important for understanding the formation mechanisms of a wide variety of oxygenates in oxygen-deficit (anaerobic) conditions and the role of the lignin side groups in pyrolysis pathways. In Part I of the current study (J. Phys. Chem. A, 2019, 123, 2570-2585), we reported a detailed potential energy (enthalpy) surface analysis of the reaction OH + p-CMA with suggestions for a variety of chemically activated, unimolecular, and bimolecular reaction pathways. In Part II of our work, we provide a detailed kinetic analysis of the major reaction channels to evaluate their significance and possible impacts on product distributions. Temperature- and pressure-dependent rate constants are calculated using the quantum Rice-Ramsperger-Kassel method and the master equation analysis for falloff and stabilization. Enthalpies of formation, entropies, and heat capacities are calculated using density functional theory and higher-level composite methods for stable molecules, radicals, and transition-state species. A significant difference between well depths for the chemically activated adduct radicals, [p-CMA-OH]*, is found for the α- and ß-carbon addition reactions to generate the 1,3- and 1,2-diol radicals, respectively. This is due to the synergistic effect from conjugation of the proximal radical center with the aromatic ring and the strong H-bonding interaction between vicinal OH groups in the ß-adduct (1,2-diol radical). Both adducts undergo isomerization and low-energy transformations, however, with different kinetic efficiencies because of the difference in stabilization energies. Reaction pathways include dissociation, intramolecular abstraction, atom and group transfers, and elimination. Of particular interest is a roaming-like low-energy dehydration reaction to form O-centered intermediate radicals. The kinetic analysis demonstrated the feasible formation of various products detected in pyrolysis experiments, suggesting that the gas-phase reactions of OH radicals can be a key process to form major products and complex oxygenates during lignin pyrolysis. Our preliminary experiments involving pyrolysis of the vaporized monomers support this basic statement. A novel mechanism for the formation of benzofuran, identified in experimentation, is also provided based on the potential conversions of hydroxyphenylacetaldehyde and corresponding isomers, which are kinetically favored products.

OH-Initiated Reactions of p-Coumaryl Alcohol Relevant to the Lignin Pyrolysis. Part I. Potential Energy Surface Analysis ⊥.

Cinnamyl alcohols such as p-coumaryl alcohol ( p-CMA) are lignin models and precursors (monolignols) and the most important primary products of lignin pyrolysis. However, the detection of monomers is not straightforward since they either undergo secondary transformations or repolymerize to contribute to the char formation. Both concerted-molecular and free-radical pathways are involved in these processes. Our recent fundamentally based theoretical and low-temperature matrix-isolation-EPR studies of cinnamyl alcohols highlighted the role of side-chain reactivity in diversity of pyrolysis products and provided a network of the chemically activated H + p-CMA reactions ( Asatryan J. Phys. Chem. A, 2017 , 121 , 3352 - 3371 ). The readily available hydroxyl radicals also can trigger a cascade of free-radical processes. Here, we present a comprehensive potential energy surface (PES) analysis of the OH + p-CMA reaction using various DFT and ab initio protocols. Since the p-CMA involves both an alkyl OH-group and a side-chain double bond, the title reaction can also serve as a relevant model for reactions of unsaturated alcohols with hydroxyl radicals to form various oxygenates including polyhydric alcohols which are abundant in nature. The newly identified pathways suggest certain alternatives to the known radical reactions. Of particular interest are the roaming-like low-energy dehydration reactions to generate a variety of O- and C-centered intermediate radicals, which are primarily transformed into the phenolic compounds observed in pyrolysis experiments. Several concerted unimolecular decomposition pathways for p-CMA are also revealed, not considered previously, such as the migration of terminal OH-group, and/or its splitting over the ipso-C and ortho-C atoms of the benzene ring to form bicyclic oxispiro- and chromene compounds represented in natural lignin.

Roaming-like Mechanism for Dehydration of Diol Radicals.

Diol radicals (DRs) are important intermediates in biocatalysis, atmospheric chemistry, and biomass combustion. They are particularly generated from photolysis of halogenated diols and addition of hydroxyl radical to a double bond of unsaturated alcohols, such as lignols. The energized DRs further isomerize/decompose to form products, including water. Aqueous-phase dehydration in radiolytic and biomimetic systems typically occurs at low temperatures, with or without catalysis, whereas the gas-phase dehydration is usually considered energetically unfavorable. In the present study, we propose a new low-energy, roaming-like mechanism based on a detailed dispersion-corrected DFT and ab initio level analysis of the gas-phase dehydration of DRs obtained from the combination of OH radicals with allyl alcohol (AA, CH2═CHCH2OH)-the simplest relevant model of the unsaturated alcohols. The roaming pathways involve a nearly dissociated OH-group, which subsequently abstracts an H atom of the remaining fragment to form water and [C3H5O] radical via a transition state (TS) with energy close to the C-O bond fission asymptote. Two types of roaming-like first-order saddle points (SP) are identified for unimolecular dehydration of 1,2- and 1,3-DR radical adducts involving either both hydroxyl groups of diol radicals to generate an oxygen-centered radical, or ß-OH group and a skeletal α-hydrogen atom of the 1,2-DR to form a resonantly stabilized hydroxyallyl radical. Two higher energy conventional (tight) transition states, along with the pathways to 1,2-OH-migration, as well as direct H-abstraction, are also identified and analyzed. Most of the traditional density functional theory methods that have been successfully employed in the literature to locate so-far-known roaming SPs were also able to identify the new mechanism, in accord with dispersion-corrected double hybrid B2PLYP-D3(BJ) and mPW2PLYPD methods involving MP2-correlation corrections. However, the MP2 method itself failed to locate any of them, which seems to be typical for MP2 method for loose TS structures, confirmed here for a flat region of PES connecting direct and roaming saddle points. However, MP2 method correctly locates an identical roaming SP for a larger p-coumaryl alcohol model involving hydroxyphenyl substituent at Cγ atom of AA. Two types of interfragmental interactions are identified that stabilize the roaming SPs: (a) H-bonding of the leaving OH radical either with the H atom of the remaining OH group, or with π-cloud of the double bond; (b) direct interaction of π-electrons with the lone-pair electrons of the heteroatom in the leaving OH group through the TS-ring. The alternative TSs are qualitatively characterized by "collinearity" angle of the OH radical attack on the O-H/C-H bonds of the substrate in abstraction-like O-H-O geometry, attributed to the improved orbital overlaps. The proposed mechanism presents broader implications to signify, particularly, a larger role in atmospheric and combustion processes, especially biomass pyrolysis.

Revisiting the polytopal rearrangements in penta-coordinate d7-metallocomplexes: modified Berry pseudorotation, octahedral switch, and butterfly isomerization.

This paper provides a first-principles theoretical investigation of the polytopal rearrangements and fluxional behavior of five-coordinate d7-transition metal complexes. Our work is primarily based on a potential energy surface analysis of the iron tetracarbonyl hydride radical HFe˙(CO)4. We demonstrate the existence of distorted coordination geometries in this prototypical system and, for the first time, introduce three general rearrangement mechanisms, which account for the non-ideal coordination. The first of these mechanisms constitutes a modified version of the Berry pseudorotation via a square-based pyramidal C4v transition state that connects two chemically identical edge-bridged tetrahedral stereoisomers of C2v symmetry. It differs from the classical Berry mechanism, which involves two regular D3h equilibrium structures and a C4v transition state. The second mechanism is related to the famous "tetrahedral jump" hypothesis, postulated by Muetterties for a number of d6 HML4 and H2ML4 complexes. Here, our study suggests two fluxional rearrangement pathways via distinct types of C2v transition states. Both pathways of this mechanism can be described as a single-ligand migration to a vacant position of an "octahedron", thus interchanging (switching) the apical and basal ligands of the initial quasi-square pyramidal isomer, which is considered as an idealized octahedron with a vacancy. Accordingly, we call this mechanism "octahedral switch". The third mechanism follows a butterfly-type isomerization featuring a key-angle deformation, and we thus call it "butterfly isomerization". It connects the quasi-square pyramidal and edge-bridged tetrahedral isomers of HFe˙(CO)4 through a distorted edge-bridged tetrahedral transition state of Cs symmetry. Our paper discusses the overall features of the isomers and rearrangement mechanisms as well as their implications. We rationalize the existence of each stationary point through an electronic structure analysis and argue their relevance for isolobal analogues of HFe˙(CO)4.

Molecular Products and Fundamentally Based Reaction Pathways in the Gas-Phase Pyrolysis of the Lignin Model Compound p-Coumaryl Alcohol.

The fractional pyrolysis of lignin model compound para-coumaryl alcohol (p-CMA) containing a propanoid side chain and a phenolic OH group was studied using the System for Thermal Diagnostic Studies at temperatures from 200 to 900 °C, in order to gain mechanistic insight into the role of large substituents in high-lignin feedstocks pyrolysis. Phenol and its simple derivatives p-cresol, ethyl-, propenyl-, and propyl-phenols were found to be the major products predominantly formed at low pyrolysis temperatures (<500 °C). A cryogenic trapping technique was employed combined with EPR spectroscopy to identify the open-shell intermediates registered at pyrolysis temperatures above 500 °C. These were characterized as radical mixtures primarily consisting of oxygen-linked conjugated radicals. A comprehensive potential energy surface analysis of p-CMA and p-CMA + H atom systems was performed using various DFT protocols to examine the possible role of concerted molecular eliminations and free-radical mechanisms in the formation of major products. Other significant unimolecular concerted reactions along with formation and decomposition of primary radicals are also described and evaluated. The calculations suggest that a set of the chemically activated secondary radical channels is relevant to the low temperature product formation under fractional pyrolysis conditions.

Radicals and molecular products from the gas-phase pyrolysis of lignin model compounds. Cinnamyl alcohol.

The experimental results on detection and identification of intermediate radicals and molecular products from gas-phase pyrolysis of cinnamyl alcohol (CnA), the simplest non-phenolic lignin model compound, over the temperature range of 400-800 °C are reported. The low temperature matrix isolation - electron paramagnetic resonance (LTMI-EPR) experiments along with the theoretical calculations, provided evidences on the generation of the intermediate carbon and oxygen centered as well as oxygen-linked, conjugated radicals. A mechanistic analysis is performed based on density functional theory to explain formation of the major products from CnA pyrolysis; cinnamaldehyde, indene, styrene, benzaldehyde, 1-propynyl benzene, and 2-propenyl benzene. The evaluated bond dissociation patterns and unimolecular decomposition pathways involve dehydrogenation, dehydration, 1,3-sigmatropic H-migration, 1,2-hydrogen shift, C-O and C-C bond cleavage processes.

Radicals from the gas-phase pyrolysis of a lignin model compound: p-coumaryl alcohol.

The intermediate radicals produced in the gas-phase pyrolysis of one of the main building blocks of lignin - p-coumaryl alcohol (p-CMA) - were investigated using the low temperature matrix isolation technique interfaced with electron paramagnetic resonance spectroscopy (LTMI-EPR). An anisotropic EPR spectrum characterized by a high g-value (>2.0080) and a relatively low saturation coefficient (∼1.40) throughout the high pyrolytic temperature region (700 to 1000 °C) was observed. Theoretical calculations revealed plausible decomposition pathways for p-CMA comprising highly delocalized aromatic radicals. The results provide evidence for a dominant role of oxygen-centered radicals during the pyrolysis of p-CMA.

Mechanism of iron carbonyl-catalyzed hydrogenation of ethylene. 1. Theoretical exploration of molecular pathways.

The hydrogenation of alkenes catalyzed by metal carbonyls is an intricate process involving reactions of various isomers of labile π- and σ-complexes, hydrides, dihydrides, and their radicals. Two general mechanisms have been suggested in the literature regarding the catalytic hydrogenation of simple alkenes by photochemically activated iron pentacarbonyl: a molecular mechanism that involves the sequential replacement of two carbonyl ligands by hydrogen and unsaturated ligands, and a radical mechanism involving the EPR-identified iron carbonyl hydride radicals. Even though significant results were obtained in numerous experiments and few theoretical studies, these mechanisms remain phenomenological, without detailed information regarding the potential energy surfaces (PES) and the elementary processes. Several major issues also remain open. It is still unclear, for instance, whether the ethane can be formed via a monomolecular reaction of ethyl hydride isomer intermediates HFe(CO)3(C2H5) or the only way to produce C2H6 is a bimolecular reaction assisted by a second ethylene. It is also uncertain if a dihydride or a dihydrogen complex is operating in olefin hydrogenation. To gain insight into these processes, a detailed theoretical examination of various PES for gas-phase reactions of ethylene with potential metallocomplex reagents to primary and secondary products (both singlet and triplet electronic states) was performed using DFT and ab initio methods. Calculations have been carried out for a set of reactions of ethylene with all possible isomers of tricarbonyliron hydrogenates, viz., dihydrides of trans-, cis-, and gauche-configurations (isomers with respect to the two hydridic atoms), and two nonclassical singlet and two triplet dihydrogen complexes, some of them being identified for the first time. The hydrogenation pathways (both molecular and radical) are shown to be strongly stereoselective and dependent on the spin configurations of the initial reagents. The combination of various dihydride isomers with C2H4 as separate reaction channels allowed us to explore relevant PES cross sections and to identify corresponding stereoregulated elementary processes. The reaction channels can alternatively start from the association of ethylene with dihydrogen tricarbonyliron complexes and may involve intersystem crossings with triplet pathways, followed by that of the corresponding singlet PES. Various interconversion and isomerization processes involving single-olefin adducts were found to precede the major ethane-elimination reactions (through both monomolecular and second-ethylene-assisted pathways). Monomolecular processes are suggested to occur under appropriate conditions. The stereospecific mechanistic results and thermochemical parameters constitute a basis for developing detailed kinetic models for iron-carbonyl catalysis.

Dihydrogen catalysis: a degradation mechanism for N2-fixation intermediates.

Molecular hydrogen plays multiple roles in activation of nitrogen. Among others, it inhibits the overall process of N(2)-reduction catalyzed by nitrogenase enzyme. The H(2)-assisted dehydrogenation and the H-atom transfer reactions (called dihydrogen catalysis, DHC) are suggested as possible mechanisms for the degradation and removal of potential intermediates formed during the reduction of nitrogen. Several iron-organic model reactions associated with the core stereospecific reaction (cis-N(2)H(2) + H(2) → N(2) + H(2) + H(2)) are examined using a comprehensive density functional theory and ab initio analysis of the corresponding potential energy surfaces. A variety of energetically feasible decomposition pathways are identified for the DHC-oxidation of iron-bound [N(x)H(y)]-species. A liberated diazene intermediate (HN═NH) is suggested to interact in situ with two proximal hydridic H-atoms of an activated (hydrided) Fe-catalyst to produce N(2) and H(2) with a low or even no activation barrier. The majority of identified pathways are shown to be highly sensitive to the electronic environment and spin configuration of metallocomplexes. The H(2)-assisted transport of a single H-atom from a bound [N(x)H(y)] moiety to either the proximal or distal (Fe, S or N) active centers of a catalyst provides an alternative degradation (interconversion) mechanism for the relevant intermediates. The two types of molecular hydrogen-assisted reactions highlighted above, namely, the H(2)-assisted dehydrogenation and the transport of H-atoms, suggest theoretical interpretations for the observed H(2)-inhibition of N(2) activation and HD formation (in the presence of D(2)). The DHC reactions of various [N(x)H(y)] moieties are expected to play significant roles in the industrial high-pressure hydrodenitrification and other catalytic processes involving the metabolism of molecular hydrogen.

Structures, internal rotor potentials, and thermochemical properties for a series of nitrocarbonyls, nitroolefins, corresponding nitrites, and their carbon centered radicals.

Structures, enthalpy (Δ(f)H°(298)), entropy (S°(T)), and heat capacity (C(p)(T)) are determined for a series of nitrocarbonyls, nitroolefins, corresponding nitrites, and their carbon centered radicals using the density functional B3LYP and composite CBS-QB3 calculations. Enthalpies of formation (Δ(f)H°(298)) are determined at the B3LYP/6-31G(d,p), B3LYP/6-31+G(2d,2p), and composite CBS-QB3 levels using several work reactions for each species. Entropy (S) and heat capacity (C(p)(T)) values from vibration, translational, and external rotational contributions are calculated using the rigid-rotor-harmonic-oscillator approximation based on the vibration frequencies and structures obtained from the density functional studies. Contribution to Δ(f)H(T), S, and C(p)(T) from the analysis on the internal rotors is included. Recommended values for enthalpies of formation of the most stable conformers of nitroacetone cc(═o)cno2, acetonitrite cc(═o)ono, nitroacetate cc(═o)no2, and acetyl nitrite cc(═o)ono are -51.6 kcal mol(-1), -51.3 kcal mol(-1), -45.4 kcal mol(-1), and -58.2 kcal mol(-1), respectively. The calculated Δ(f)H°(298) for nitroethylene c═cno2 is 7.6 kcal mol(-1) and for vinyl nitrite c═cono is 7.2 kcal mol(-1). We also found an unusual phenomena: an intramolecular transfer reaction (isomerization) with a low barrier (3.6 kcal mol(-1)) in the acetyl nitrite. The NO of the nitrite (R-ONO) in CH(3)C(═O')ONO moves to the C═O' oxygen in a motion of a stretching frequency and then a shift to the carbonyl oxygen (marked as O' for illustration purposes).

Radicals from the gas-phase pyrolysis of catechol. 2. Comparison of the pyrolysis of catechol and hydroquinone.

Formation of radicals from the pyrolysis of catechol (CT) and hydroquinone (HQ) over a temperature range of 350-900 °C was studied using low-temperature matrix isolation electron paramagnetic resonance (LTMI EPR) spectroscopy. Comparative analysis of the pyrolysis mechanisms of these isomeric compounds was performed, and the role of semiquinone-type carrier radicals was studied. Pathways of unimolecular decomposition of intermediate radicals and molecular products were identified from the examination of the potential energy surface of catechol calculated at B3LYP hybrid density functional theory and composite CBS-QB3 levels. The results were compared with the experimental observations and mechanistic pathways previously developed for the pyrolysis of hydroquinone.

Quantum chemical study of the acrolein (CH2CHCHO) + OH + O2 reactions.

Acrolein, a beta-unsaturated (acrylic) aldehyde, is one of the simplest multifunctional molecules, containing both alkene and aldehyde groups. Acrolein is an atmospheric pollutant formed in the photochemical oxidation of the anthropogenic VOC 1,3-butadiene, and serves as a model compound for methacrolein (MACR) and methyl vinyl ketone (MVK), the major oxidation products of the biogenic VOC isoprene. In addition, acrolein is involved in combustion and biological oxidation processes. This study presents a comprehensive theoretical analysis of the acrolein + OH + O(2) addition reactions, which is a key photochemical oxidation sequence, using the G3SX and CBS-QB3 theoretical methods. Both ab initio protocols provide relatively similar results, although the CBS-QB3 method systematically under-predicts literature heats of formation using atomization enthalpies, and also provides lower transition state barrier heights. Several new low-energy pathways for unimolecular reaction of the acrolein-OH-O(2) radicals are identified, with energy at around or below that of the acrolein-OH isomers + O(2). In each case these novel reactions have the potential to reform the hydroxyl radical (OH) and form coproducts that include glyoxal, glycolaldehyde (HOCH(2)CHO), formaldehyde (HCHO), CO, and substituted epoxides. Analogous reaction schemes are developed for the photochemical oxidation of MACR and MVK, producing a number of observed oxidation products. The reaction MACR + OH + O(2) --> hydroxyacetone + OH + CO is expected to be of particular importance. This study also proposes that O(2) addition to chemically activated acrolein-OH adducts can provide prompt regeneration of OH in the atmospheric oxidation of acrolein, via a double activation mechanism. This mechanism can also be extended to isoprene, MVK, and MACR. The importance of the novel chemistry revealed here in the atmospheric oxidation of acrolein and other structurally related OVOCs and VOCs requires further investigation. Additionally, a critical evaluation of the acrolein heat of formation is presented, and a new value of -16.7 +/- 1.0 kcal mol(-1) is recommended along with other thermochemical properties, from a W1 level calculation.

Thermochemical properties of exo-tricyclo[5.2.1.0(2,6)]decane (JP-10 jet fuel) and derived tricyclodecyl radicals.

exo-Tricyclo[5.2.1.0(2,6)]decane (TCD) or exo-tetrahydrodicyclopentadiene is the principal component of the high-energy density hydrocarbon fuel commonly identified as JP-10. Thermodynamic parameters for the parent TCD molecule and of all the tricyclodecyl radicals corresponding to the loss of hydrogen atoms from different carbons sites (TCD-Ri with i indicating the given carbon center) are determined using several density functional theory and G3MP2B3 and CBS-QB3 higher level composite computational chemistry methods. Five isodesmic work reactions, three involving bridged hydrocarbon reference molecules with similar ring strains, are employed to produce a cancelation of systematic calculation errors in evaluation of standard, gas-phase formation enthalpies at 298 K. Delta(f)H degrees (298) for TCD is found to be -19.5 +/- 1.3 kcal mol(-1), which is several kcal mol(-1) lower than the commonly used values. C(i)-H bond energies for corresponding TCD carbon sites are evaluated as follows: TCD-R1, 107.2; TCD-R2, 100.1; TCD-R3, 98.0; TCD-R4, 98.5; TCD-R9, 98.7; TCD-R10, 104.1 kcal mol(-1). Results from use of five different DFT methods are in very good agreement with composite level values for all work reactions used for the radicals. The exo and endo isomers of TCD are both determined to have chair and boat conformers.

Chain branching and termination in the low-temperature combustion of n-alkanes: 2-pentyl radical + O2, isomerization and association of the second O2.

Association of alkyl radicals with ground-state oxygen (3)Sigma(g)(+)(O(2)) generates chemically activated peroxy intermediates, which can isomerize or further react to form new products before collisional stabilization. The lowest-energy reaction (approximately 19 kcal mol(-1)) for alkylperoxy derivatives of C(3) and larger n-hydrocarbons is an isomerization (intramolecular H-atom transfer) that forms a hydroperoxide alkyl radical, and there is a approximately 30 kcal mol(-1) barrier path to olefin plus HO(2), which is a termination step at lower temperatures. The low-energy-barrier product, hydroperoxide alkyl radical intermediate, can experience additional chemical activation via association with a second oxygen molecule, where there are three important paths that result in chain branching. The competition between this HO(2) + olefin termination step of the first O(2) association and the chain branching processes from the second chemical activation step plays a dominant role at temperatures below 1000 K. Secondary n-pentyl radicals are used in this study as surrogates to analyze the thermochemistry and detailed kinetics of the chemical activation and stabilized adduct reactions important to chain branching and termination. As these radicals provide six- member ring transition states for H-atom transfer between secondary carbons, they represent the detailed kinetics of larger alkane radicals, such as the common fuel components n-heptane and n-decane. Comprehensive potential energy diagrams developed from multilevel CBS-QB3, G3MP2, and CBS-APNO and single-level ab initio and density functional theory methods are used to analyze secondary 2-pentyl (n-pentan-2-yl) and interrelated 2-hydroperoxide-pentan-4-yl radical interactions with O(2). The thermochemistry and kinetics of the chemical activation and stabilized adduct reactions important to chain branching and termination are reported and discussed. Results show that the chain branching reactions have faster kinetics in this system because the barriers are lower than those observed in ethyl and propyl radical plus O(2) reactions; consequently, the branching is predicted to be more important. The lower barriers for branching result in less competition from the termination (HO(2) + olefin) path in this larger radical. Several nontraditional reaction channels not previously considered in the literature are identified. A pathway is suggested to explain the formation of a unique trioxane product observed experimentally.

Formation and decomposition of chemically activated and stabilized hydrazine.

Recombination of two amidogen radicals, NH(2) (X(2)B1), is relevant to hydrazine formation, ammonia oxidation and pyrolysis, nitrogen reduction (fixation), and a variety of other N/H/X combustion, environmental, and interstellar processes. We have performed a comprehensive analysis of the N(2)H(4) potential energy surface, using a variety of theoretical methods, with thermochemical kinetic analysis and master equation simulations used to treat branching to different product sets in the chemically activated NH(2) + NH(2) process. For the first time, iminoammonium ylide (NH(3)NH), the less stable isomer of hydrazine, is involved in the kinetic modeling of N(2)H(4). A new, low-energy pathway is identified for the formation of NH(3) plus triplet NH, via initial production of NH(3)NH followed by singlet-triplet intersystem crossing. This new reaction channel results in the formation of dissociated products at a relatively rapid rate at even moderate temperatures and above. A further novel pathway is described for the decomposition of activated N(2)H(4), which eventually leads to the formation of the simple products N(2) + 2H(2), via H(2) elimination to cis-N(2)H(2). This process, termed as "dihydrogen catalysis", may have significant implications in the formation and decomposition chemistry of hydrazine and ammonia in diverse environments. In this mechanism, stereoselective attack of cis-N(2)H(2) by molecular hydrogen results in decomposition to N(2) with a fairly low barrier. The reverse termolecular reaction leading to the gas-phase formation of cis-N(2)H(2) + H(2) achieves non-heterogeneous catalytic nitrogen fixation with a relatively low activation barrier (77 kcal mol(-1)), much lower than the 125 kcal mol(-1) barrier recently reported for bimolecular addition of H(2) to N(2). This termolecular reaction is an entropically disfavored path, but it does describe a new means of activating the notoriously unreactive N(2). We design heterogeneous analogues of this reaction using the model compound (CH(3))(2)FeH(2) as a source of the H(2) catalyst and apply it to the decomposition of cis-diazene. The reaction is seen to proceed via a topologically similar transition state, suggesting that our newly described mechanism is general in nature.

Radicals from the gas-phase pyrolysis of catechol: 1. o-Semiquinone and ipso-catechol radicals.

The formation of environmentally persistent free radicals (EPFRs) from the gas-phase pyrolysis of catechol (CT) was studied over a temperature range of 400-750 degrees C using the technique of low-temperature matrix isolation electron paramagnetic resonance (LTMI-EPR) spectroscopy. A split singlet EPR spectrum with a g value of 2.0052 was observed. To aid in the interpretation of this spectrum, a detailed analysis of the potential energy surface of CT decomposition pathways was performed employing CBS-QB3 multilevel and DFT individual methods. The energetically favored channels were the formation of ipso- and alpha-CT isomers of CT as well as o-semiquinone (o-SQ) radicals from ipso- and alpha-CT. ipso-CT as well as open ipso-CT radicals were apparently unstable intermediates that could not be accumulated in sufficiently high concentrations to be detected by EPR. The calculated EPR spectrum of o-SQ radical is consistent with the formation of an oxygen-centered radical with a high g value observed experimentally. The hyperfine splitting of the observed spectrum can be attributed to the formation of hydrogen bonds in radical dimers. The lack of experimental observation of o-benzoquinone, an anticipated pyrolysis product, has been explained based on theoretical calculations.