Tropospheric oxidation of ethyne and But-2-yne. 1. Theoretical mechanistic study

This paper (part 1) and the following one (part 2) aim to assess the viability of some tropospheric oxidation channels for two symmetrical alkynes, ethyne (acetylene) and but-2-yne. Paper 1 defines the features of the DFT(B3LYP)/6-311G(3df,2p) energy hypersurface and qualitatively considers the practicability of different pathways through the estimate of free energy barriers. Paper 2 will assess this in more detail by way of master equation simulations. Oxidized in the presence of HO and O2 (with the possible intervention of NO), ethyne and but-2-yne are known to produce mainly glyoxal or dimethylglyoxal and, to a lesser extent, formic or acetic acid. The initial attack by HO gives an adduct, from which several pathways (1a-c, 2a-e) originate. Pathway 1a passes through the 2-oxoethyl (vinoxyl) radical, or the analogous dimethyl-substituted intermediate, which could in principle undergo O2 addition (and subsequently, but through a demanding step, give the dialdehydes). However, in paper 2 it is assessed that the vinoxyl, as a nonthermalized intermediate, will preferentially follow unimolecular pathways to ketene or acetyl. Pathway 2a is the most important pathway: a very steep free energy cascade, started by O2 addition to the initial HO adduct with a concerted barrierless 1,5 H shift, gives a hydroperoxyalkenyloxyl radical intermediate. Peroxy bond cleavage finally produces the dialdehydes and regenerates HO. Pathways 2b and 2c originate from O2 addition to the initial HO adduct and produce, via different ring closures, either dioxetanyl or alkyl dioxiranyl radicals, respectively. Two subsequent fragmentations occur in both cases and give the carboxylic acids and a carbonyl radical, which can indirectly generate hydroxyl. Two further pathways (1c and 2e) see NO intervention onto the peroxyl radicals formed along pathways 1 and 2. Both could enhance dialdehyde production, while simultaneously depressing the carboxylic acid yield.     

Infrared measurements and calculations on H2O.HO

We have measured the infrared spectrum of H2O.HO in argon matrices at 11.5 +/- 0.5 K. We have also calculated the vibrational frequencies and intensities of the H2O.HO complex. As a result of these measurements and calculations, we have assigned a previously unassigned absorption band at 3442.1 cm-1 to the OH stretch in the radical complexed to the water molecule. This absorption originates from a complex that is situated in a different site within the argon matrix to those absorptions already assigned to this vibration at 3452.2 and 3428.0 cm-1. We observe a decrease in intensity of the OH radical stretching vibration of the H2O.HO complex upon isotopic substitution of D for H that agrees well with our calculations.     

Exploration of the potential energy surfaces, prediction of atmospheric concentrations, and prediction of vibrational spectra for the HO2...(H2O)n (n = 1-2) hydrogen bonded complexes

The hydroperoxy radical (HO2) plays a critical role in Earth's atmospheric chemistry as a component of many important reactions. The self-reaction of hydroperoxy radicals in the gas phase is strongly affected by the presence of water vapor. In this work, we explore the potential energy surfaces of hydroperoxy radicals hydrogen bonded to one or two water molecules, and predict atmospheric concentrations and vibrational spectra of these complexes. We predict that when the HO2 concentration is on the order of 10(8) molecules x cm(-3) at 298 K, that the number of HO2...H2O complexes is on the order of 10(7) molecules x cm(-3) and the number of HO2...(H2O)2 complexes is on the order of 10(6) molecules x cm(-3). Using the computed abundance of HO2...H2O, we predict that, at 298 K, the bimolecular rate constant for HO2...H2O + HO2 is about 10 times that for HO2 + HO2.     

Dimethylselenide as a probe for reactions of halogenated alkoxyl radicals in aqueous solution. Degradation of dichloro- and dibromomethane

Using pulse radiolysis and steady-state gamma-radiolysis techniques, it has been established that, in air-saturated aqueous solutions, peroxyl radicals CH 2HalOO (*) (Hal = halogen) derived from CH 2Cl 2 and CH 2Br 2 react with dimethyl selenide (Me 2Se), with k on the order of 7 x 10 (7) M (-1) s (-1), to form HCO 2H, CH 2O, CO 2, and CO as final products. An overall two-electron oxidation process leads directly to dimethyl selenoxide (Me 2SeO), along with oxyl radical CH 2HalO (*). The latter subsequently oxidizes another Me 2Se molecule by a much faster one-electron transfer mechanism, leading to the formation of equal yields of CH 2O and the dimer radical cation (Me 2Se) 2 (*+). In absolute terms, these yields amount to 18% and 28% of the CH 2ClO (*) and CH 2BrO (*) yields, respectively, at 1 mM Me 2Se. In competition, CH 2HalO (*) rearranges into (*)CH(OH)Hal. These C-centered radicals react further via two pathways: (a) Addition of an oxygen molecule leads to the corresponding peroxyl radicals, that is, species prone to decomposition into H (+)/O 2 (*-) and formylhalide, HC(O)Hal, which further degrades mostly to H (+)/Hal (-) and CO. (b) Elimination of HHal yields the formyl radical H-C(*)=O with a rate constant of about 6 x 10 (5) s (-1) for Hal = Cl. In an air-saturated solution, the predominant reaction pathway of the H-C(*)=O radical is addition of oxygen. The formylperoxyl radical HC(O)OO (*) thus formed reacts with Me 2Se via an overall two-electron transfer mechanism, giving additional Me 2SeO and formyloxyl radicals HC(O)O(*). The latter rearrange via a 1,2 H-atom shift into (*)C(O)OH, which reacts with O2 to give CO2 and O2(*)(-). The minor fraction of H-C(*)=O undergoes hydration, with an estimated rate constant of k approximately 2 x 10(5) s(-1). The resulting HC(*)(OH)2 radical, upon reaction with O2, yields HCO 2H and H (+)/O2(*-). Some of the conclusions about the reactions of halogenated alkoxyl radicals are supported by quantum chemical calculations [B3LYP/6-31G(d,p)] taking into account the influence of water as a dielectric continuum [by the self-consistent reaction field polarized continuum model (SCRF=PCM) technique]. Based on detailed product studies, mechanisms are proposed for the free-radical degradation of CH 2Cl 2 and CH 2Br 2 in the presence of oxygen and an electron donor (namely, Me 2Se in this study), and properties of the reactive intermediates are discussed.     

Elucidation of the mechanisms of peroxyl radical reactions in aqueous solutions using the pulse radiolysis technique

In the investigation of peroxyl radicals the pulse radiolysis technique can be used with some advantage to determine the rate of their unimolecular or bimolecular decay. If the identities of the products of the peroxyl radical reactions are known, pulse radiolysis often provides evidence for mechanistic details. The absorptions of the peroxyl radicals are neither very specific nor strong and optical detection is usually of little help. However, there are many peroxyl radical reactions which result in the formation of HO ₂ ^. /H+O ₂ ^. (pK_a(HO ₂ ^. )=4.7) or other acids. Thus in neutral and alkaline solutions such species can be monitored even quantitatively by the pulse conductometric method. Furthermore, O ₂ ^. can be detected by its rapid reaction with tetranitromethane which yields the strongly absorbing nitroform anion. Since O ₂ ^. is only a short-lived intermediate in neutral solutions, it can be distinguished from permanent acids which are often formed in peroxyl radical reactions. In alkaline solutions, where O ₂ ^. is more stable, superoxide dismutase might be used with advantage to reduce its lifetime and to determine the yield of permanent acids. Some details of the fate of the peroxyl radicals derived from acetate, the -hydroxyethyl-peroxyl radicals, and the cyclopentylperoxyl radicals will be reviewed.     

An ab initio/RRKM study of product branching ratios in the photodissociation of buta-1,2- and -1,3-dienes and but-2-yne at 193 nm

Ab initio G2M(MP2)//B3LYP/6-311G** calculations have been performed to investigate the reaction mechanism of photodissociation of buta-1,2- and -1,3-dienes and but-2-yne after their internal conversion into the vibrationally hot ground electronic state. The detailed study of the potential-energy surface was followed by microcanonical RRKM calculations of energy-dependent rate constants for individual reaction steps (at 193 nm photoexcitation and under collision-free conditions) and by solution of kinetic equations aimed at predicting the product branching ratios. For buta-1,2-diene, the major dissociation channels are found to be the single Cbond;C bond cleavage to form the methyl and propargyl radicals and loss of hydrogen atoms from various positions to produce the but-2-yn-1-yl (p1), buta-1,2-dien-4-yl (p2), and but-1-yn-3-yl (p3) isomers of C(4)H(5). The calculated branching ratio of the CH(3) + C(3)H(3)/C(4)H(5) + H products, 87.9:5.9, is in a good agreement with the recent experimental value of 96:4 (ref. 21) taking into account that a significant amount of the C(4)H(5) product undergoes secondary dissociation to C(4)H(4) + H. The isomerization of buta-1,2-diene to buta-1,3-diene or but-2-yne appears to be slower than its one-step decomposition and plays only a minor role. On the other hand, the buta-1,3-diene-->buta-1,2-diene, buta-1,3-diene-->but-2-yne, and buta-1,3-diene-->cyclobutene rearrangements are significant in the dissociation of buta-1,3-diene, which is shown to be a more complex process. The major reaction products are still CH(3) + C(3)H(3), formed after the isomerization of buta-1,3-diene to buta-1,2-diene, but the contribution of the other radical channels, C(4)H(5) + H and C(2)H(3) + C(2)H(3), as well as two molecular channels, C(2)H(2) + C(2)H(4) and C(4)H(4) + H(2), significantly increases. The overall calculated C(4)H(5) + H/CH(3) + C(3)H(3)/C(2)H(3) + C(2)H(3)/C(4)H(4) + H(2)/C(2)H(2) + C(2)H(4) branching ratio is 24.0:49.6:4.6:6.1:15.2, which agrees with the experimental value of 20:50:8:2:2022 within 5 % margins. For but-2-yne, the one-step decomposition pathways, which include mostly H atom loss to produce p1 and, to a minor extent, molecular hydrogen elimination to yield methylethynylcarbene, play an approximately even role with that of the channels that involve the isomerization of but-2-yne to buta-1,2- or -1,3-dienes. p1 + H are the most important reaction products, with a branching ratio of 56.6 %, followed by CH(3) + C(3)H(3) (23.8 %). The overall C(4)H(5) + H/CH(3) + C(3)H(3)/C(2)H(3) + C(2)H(3)/C(4)H(4) + H(2)/C(2)H(2) + C(2)H(4) branching ratio is predicted as 62.0:23.8:2.5:5.7:5.6. Contrary to buta-1,2- and -1,3-dienes, photodissociation of but-2-yne is expected to produce more hydrogen atoms than methyl radicals. The isomerization mechanisms between various isomers of the C(4)H(6) molecule including buta-1,2- and -1,3-dienes, but-2-yne, 1-methylcyclopropene, dimethylvinylidene, and cyclobutene have been also characterized in detail.     

Oxidation of 2-propanol and cyclohexane by the reagent "hydrogen peroxide-vanadate anion-pyrazine-2-carboxylic acid": kinetics and mechanism

The vanadate anion in the presence of pyrazine-2-carboxylic acid (PCA [identical with] pcaH) efficiently catalyzes the oxidation of 2-propanol by hydrogen peroxide to give acetone. UV-vis spectroscopic monitoring of the reaction as well as the kinetics lead to the conclusion that the crucial step of the process is the monomolecular decomposition of a diperoxovanadium(V) complex containing the pca ligand to afford the peroxyl radical, HOO(.-) and a V(IV) derivative. The rate-limiting step in the overall process may not be this (rapid) decomposition itself but (prior to this step) the slow hydrogen transfer from a coordinated H2O2 molecule to the oxygen atom of a pca ligand at the vanadium center: "(pca)(O=)V...O2H2" --> "(pca)(HO-)V-OOH". The V(IV) derivative reacts with a new hydrogen peroxide molecule to generate the hydroxyl radical ("V(IV)" + H2O2 --> "V(V)" + HO(-) + HO(.-)), active in the activation of isopropanol: HO(.-) + Me2CH(OH) --> H2O + Me2C(.-)(OH). The reaction with an alkane, RH, in acetonitrile proceeds analogously, and in this case the hydroxyl radical abstracts a hydrogen atom from the alkane: HO(.-) + RH --> H2O + R(.-). These conclusions are in a good agreement with the results obtained by Bell and co-workers (Khaliullin, R. Z.; Bell, A. T.; Head-Gordon, M. J. Phys. Chem. B 2005, 109, 17984-17992) who recently carried out a density functional theory study of the mechanism of radical generation in the reagent under discussion in acetonitrile.     

Effects of a single water molecule on the OH + H2O2 reaction

The effect of a single water molecule on the reaction between H(2)O(2) and HO has been investigated by employing MP2 and CCSD(T) theoretical approaches in connection with the aug-cc-PVDZ, aug-cc-PVTZ, and aug-cc-PVQZ basis sets and extrapolation to an ∞ basis set. The reaction without water has two elementary reaction paths that differ from each other in the orientation of the hydrogen atom of the hydroxyl radical moiety. Our computed rate constant, at 298 K, is 1.56 × 10(-12) cm(3) molecule(-1) s(-1), in excellent agreement with the suggested value by the NASA/JPL evaluation. The influence of water vapor has been investigated by considering either that H(2)O(2) first forms a complex with water that reacts with hydroxyl radical or that H(2)O(2) reacts with a previously formed H(2)O·OH complex. With the addition of water, the reaction mechanism becomes much more complex, yielding four different reaction paths. Two pathways do not undergo the oxidation reaction but an exchange reaction where there is an interchange between H(2)O(2)·H(2)O and H(2)O·OH complexes. The other two pathways oxidize H(2)O(2), with a computed total rate constant of 4.09 × 10(-12) cm(3) molecule(-1) s(-1) at 298 K, 2.6 times the value of the rate constant of the unassisted reaction. However, the true effect of water vapor requires taking into account the concentration of the prereactive bimolecular complex, namely, H(2)O(2)·H(2)O. With this consideration, water can actually slow down the oxidation of H(2)O(2) by OH between 1840 and 20.5 times in the 240-425 K temperature range. This is an example that demonstrates how water could be a catalyst in an atmospheric reaction in the laboratory but is slow under atmospheric conditions.     

Direct ESR detection of pentadienyl radicals and peroxyl radicals in lipid peroxidation: mechanistic insight into regioselective oxygenation in lipoxygenases

Well-resolved ESR spectra of free pentadienyl radicals have been observed under photoirradiation of di-tert-butylperoxide (Bu(t)OOBu(t)) and polyunsaturated fatty acids in the absence of O(2), allowing us to determine the hfc values. The hfc values of linoleyl radical indicate that the spin density is the largest at the C-11 position. The linoleyl radical is readily trapped by O(2) to produce the peroxyl radical (11-HPO.) in which O(2) is added mainly at the C-11 position of the pentadienyl radical as indicated by the comparison of the ESR spectra of peroxyl radicals derived from linoleic acid and [11,11-(2)H(2)]linoleic acid. The peroxyl radical (13-HPO.), which is initially formed by the hydrogen abstraction from 13-(S)-hydroperoxy-9(Z),11(E)-octadecadienoic acid (13-HPOD) by Bu(t)O., is found to isomerize to 11-HPO. via removal of O(2) from 13-HPO. and addition of O(2) to linoleyl radical to produce 11-HPO. . This finding supports an idea of O(2) entering via a specific protein channel, which determines the stereo- and regiochemistry of the biradical combination between O(2) and linoleyl radical in lipoxygenases.     

Kinetics of the reaction C2H5 + HO2 by time-resolved mass spectrometry

The overall rate constant for the radical-radical reaction C2H5 + HO2 --> products has been determined at room temperature by means of time-resolved mass spectrometry using a laser photolysis/flow reactor combination. Excimer laser photolysis of gas mixtures containing ethane, hydrogen peroxide, and oxalyl chloride was employed to generate controlled concentrations of C2H5 and HO2 radicals by the fast H abstraction reactions of the primary radicals Cl and OH with C2H6 and H2O2, respectively. By careful adjustments of the radical precursor concentrations, the title reaction could be measured under almost pseudo-first-order conditions with the concentration of HO2 in large excess over that of C2H5. From detailed numerical simulations of the measured concentration-time profiles of C2H5 and HO2, the overall rate constant for the reaction was found to be k1(293 K) = (3.1 +/- 1.0) x 10(13) cm3 mol(-1) s(-1). C2H5O could be confirmed as a direct reaction product.     

A temperature-dependent relative-rate study of the OH initiated oxidation of n-butane: the kinetics of the reactions of the 1- and 2-butoxy radicals

The kinetics of the reactions of 1-and 2-butoxy radicals have been studied using a slow-flow photochemical reactor with GC-FID detection of reactants and products. Branching ratios between decomposition, CH3CH(O*)CH2CH3 --> CH3CHO + C2H5, reaction (7), and reaction with oxygen, CH3CH(O*)CH2CH3+ O2 --> CH3C(O)C2H5+ HO2, reaction (6), for the 2-butoxy radical and between isomerization, CH3CH2CH2CH2O* --> CH2CH2CH2CH2OH, reaction (9), and reaction with oxygen, CH3CH2CH2CH2O* + O2 --> C3H7CHO + HO2, reaction (8), for the 1-butoxy radical were measured as a function of oxygen concentration at atmospheric pressure over the temperature range 250-318 K. Evidence for the formation of a small fraction of chemically activated alkoxy radicals generated from the photolysis of alkyl nitrite precursors and from the exothermic reaction of 2-butyl peroxy radicals with NO was observed. The temperature dependence of the rate constant ratios for a thermalized system is given by k7/k6= 5.4 x 10(26) exp[(-47.4 +/- 2.8 kJ mol(-1))/RT] molecule cm(-3) and k9/k8= 1.98 x 10(23) exp[(-22.6 +/- 3.9 kJ mol(-1))/RT] molecule cm(-3). The results agree well with the available experimental literature data at ambient temperature but the temperature dependence of the rate constant ratios is weaker than in current recommendations.     

Reactions of hydroxyl radicals with alkenes in low-temperature matrices

The reactions of hydroxyl radicals with a number of stable alkenes have been studied in low-temperature matrices. The reactions were initiated by broad band UV-visible irradiation of matrices containing H2O2, and the alkene under investigation. The hydroxyalkyl radical products were identified principally by comparison of their spectra with the spectra of corresponding stable alcohols. Accordingly, IR spectra were recorded for the following series of alcohols isolated in argon matrices--methanol, ethanol, ethanol-d6, propan-1-ol, propan-2-ol, butan-2-ol, 2-methylpropan-1-ol (iso-butyl alcohol), 2-methylpropan-2-ol (tert-butyl alcohol), 2-methylbutan-2-ol (tert-amyl alcohol), 3-methylbutan-2-ol and 2,3-dimethylbutan-2-ol. The hydroxyalkyl radicals, which appear to be formed from the alkenes studied were as follows--from ethene, 2-hydroxyethyl radical: from cis- or trans-but-2-ene. 1-methyl-2-hydroxypropyl radical; from propene, 1-methyl-2-hydroxyethyl and 2-hydroxypropyl radicals; from but-1-ene. 1-hydroxymethylpropyl and 2-hydroxybutyl radicals; from 2-methylpropene (iso-butene), 1,1-dimethyl-2-hydroxyethyl and 2-methyl-2-hydroxypropyl radicals; the radical products from buta-1,3-diene and isoprene could not be identified. In the cases, where two radical products were possible, i.e. when propene, but-1-ene or 2-methylpropene were the substrates, it was found that the concentration of the secondary or tertiary radical always exceeded that of the primary radical. However, the relative concentration of these radicals appears to be determined by subsequent photolysis to give carbonyl compounds. There seems, therefore, to be little preference for the secondary and tertiary radicals over the primary radicals in the primary addition process. Comments on the mechanism of the transformation from radical to carbonyl compound based upon identification of intermediates within the matrix and isotopic substitution experiments are made. The characterisation of the 2-hydroxyethyl radical has been backed up by experiments utilising isotopic substitution with 13C and D (2H). The other radicals have been identified with varying degrees of certainty. Those radicals, which are observed at the highest concentration and which are, therefore, characterised more certainly are--2-hydroxyethyl (1), from ethene: 1-methyl-2-hydroxypropyl (2), from cis- and trans-but-2-ene; 1-methyl-2-hydroxyethyl (3), from propene; 1-hydroxymethylpropyl (5), from but-1-ene; and 1,1- dimethyl-2-hydroxyethyl (8), from 2-methylpropene.     

Kinetics of alpha-hydroxy-alkylperoxyl radicals in oxidation processes. HO2*-initiated oxidation of ketones/aldehydes near the tropopause

A comparative theoretical study is presented on the formation and decomposition of alpha-hydroxy-alkylperoxyl radicals, Q(OH)OO* (Q = RR'C:), important intermediates in the oxidation of several classes of oxygenated organic compounds in atmospheric chemistry, combustion, and liquid-phase autoxidation of hydrocarbons. Detailed potential energy surfaces (PESs) were computed for the HOCH2O2* <==>HO2* + CH2O reaction and its analogues for the alkyl-substituted RCH(OH)OO* and R2C(OH)OO* and the cyclic cyclo-C6H10(OH)OO*. The state-of-the-art ab initio methods G3 and CBS-QB3 and a nearly converged G2M//B3LYP-DFT variant were found to give quasi-identical results. On the basis of the G2M//B3LYP-DFT PES, the kinetics of the approximately equal to 15 kcal/mol endothermal alpha-hydroxy-alkylperoxyl decompositions and of the reverse HO2*+ ketone/aldehyde reactions were evaluated using multiconformer transition state theory. The excellent agreement with the available experimental (kinetic) data validates our methodologies. Contrary to current views, HO2* is found to react as fast with ketones as with aldehydes. The high forward and reverse rates are shown to lead to a fast Q(OH)OO* <==>HO2* + carbonyl quasi-equilibrium. The sizable [Q(OH)OO*]/[carbonyl] ratios predicted for formaldehyde, acetone, and cyclo-hexanone at the low temperatures (below 220 K) of the earth's tropopause are shown to result in efficient removal of these carbonyls through fast subsequent Q(OH)OO* reactions with NO and HO2*. IMAGES model calculations indicate that at the tropical tropopause the HO2*-initiated oxidation of formaldehyde and acetone may account for 30% of the total removal of these major atmospheric carbonyls, thereby also substantially affecting the hydroxyl and hydroperoxyl radical budgets and contributing to the production of formic and acetic acids in the upper troposphere and lower stratosphere. On the other hand, an RRKM-master equation analysis shows that hot alpha-hydroxy-alkylperoxyls formed by the addition of O(2) to C(1)-, C(2)-, and C(3)-alpha-hydroxy-alkyl radicals will quasi-uniquely fragment to HO2* plus the carbonyl under all atmospheric conditions.     

Organophosphorus chemistry. Part 21 [1]. Insertion of olefins into P  CF3 bonds

Tris(trifluoromethyl)phosphine and ethylene reacted efficiently under u.v. irradiation to give 3,3,3-trifluoropropylbis(trifuomothyl) phosphine in good yield. With vinyl fluoride, vinylidene fluoride, and propene the reaction was regioselective rather than regiospecific, and the yield of 1:1 adduct was low. In these reactions, and in those with vinyl chloride, but-1-ene, and hexafluoropropene, in which only traces of 1:1-adduct could be detected, the bulk of the olefin and of the phosphine was recovered, and numerous by-products consistent with radical intermediates were identified. With propyne, 1,1,1-trifluoro-3-bis(trifluoromethyl)phosphino-cis-but-2-ene was obtained in moderate yield, but no reaction occurred between the phosphine and either but-2-yne or hexafluorcbut-2-yne. Tris(trifluoromethyl)phosphine oxide did not form an adduct with ethylene, tetrafluoroethylene, or propyne.Bis(trifluoromethyl)phosphine and dimethylphosphine both reacted readily under u.v. irradiation with 3,3,3-trifluoropropene, the phosphinyl radical attacking the terminal carbon in each case.     

Gas-phase ion-molecule reactions using regioselectively generated radical cations to model oxidative damage and probe radical sites in peptides

Collision induced dissociation (CID) of sodiated peptide derivatives containing a nitrate ester functionality was used to regiospecifically generate three isomeric radicals of the model peptide Bz-Ala-Gly-OMe corresponding to radicals formed at: C(α) of the alanine residue [4+Na](+); C(α) of the glycine residue [5+Na](+); and the side chain of alanine [6+Na](+). The ion-molecule reactions of these peptide radicals were examined to model oxidative damage to peptides and to probe whether the radical sites maintain their integrity or whether they isomerise via intramolecular hydrogen atom transfer (HAT). Only [6+Na](+) is reactive towards O(2), forming the peroxyl radical [7+Na](+), which loses O(2), HO˙ and HO(2)˙ under CID. The radical ion [7 + Na](+) abstracts a hydrogen atom from 4-fluorothiophenol to form the hydroperoxide [8+Na](+), which upon CID fragments via the combined loss of HO˙ and CH(2)O. In contrast, all three of the isomeric sodiated radicals react with NO˙ and NO(2)˙ to form adducts. CID of the NO adducts only regenerates the radicals via NO˙ loss, thus providing no structural information. In contrast, CID of the NO(2) adducts gives rise to a range of product ions and the spectra are different for each of the three adducts, suggesting that the isomeric radicals [4+Na](+), [5+Na](+) and [6+Na](+) are produced as discrete species. Finally, CID of the NO(2) adducts was used to probe the rearrangement of the radicals [4+Na](+), [5+Na](+) and [6+Na](+) prior to their reaction with NO(2)˙: [6 + Na](+) rearranges to a mixture of [4+Na](+) and [5+Na](+) while [5+Na](+) rearranges to [4+Na](+).     

Reactive oxygen and nitrogen species (RONS) scavenging reactions of o-vanillin: Pulse radiolysis and stopped flow studies

Reactions of peroxyl radicals and peroxynitrite with o-vanillin (2-hydroxy 3-methoxy benzaldehyde), a positional isomer of the well-known dietary compound vanillin, were studied to understand the mechanisms of its free radical scavenging action. Trichloromethylperoxyl radicals (CCl₃O ₂ ^· ) were used as model peroxyl radicals and their reactions with o-vanillin were studied using nanosecond pulse radiolysis technique with absorption detection. The reaction produced a transient with a bimolecular rate constant of approx. 10⁵ M⁻¹s⁻¹, having absorption in the 400–500 nm region with a maximum at 450 nm. This spectrum looked significantly different from that of phenoxyl radicals of o-vanillin produced by the one-electron oxidation by azide radicals. The spectra and decay kinetics suggest that peroxyl radical reacts with o-vanillin mainly by forming a radical adduct. Peroxynitrite reactions with o-vanillin at pH 6.8 were studied using a stopped-flow spectrophotometer. o-Vanillin reacts with peroxynitrite with a bimolecular rate constant of 3 × 10³ M⁻¹s⁻¹. The reaction produced an intermediate having absorption in the wavelength region of 300–500 nm with a absorption maximum at 420 nm, that subsequently decayed in 20 s with a first-order decay constant of 0.09 s⁻¹. The studies indicate that o-vanillin is a very efficient scavenger of peroxynitrite, but not a very good scavenger of peroxyl radical. The reactions take place through the aldehyde and the phenolic OH group and are significantly different from other phenolic compounds.     

A mechanistic study of the 2-thienylmethyl + HO2 radical recombination reaction

Radical recombination reactions are important in the combustion of fuel oils. Shale oil contains alkylated heteroaromatic species, the simplest example of which is the 2-thienylmethyl radical. The ab initio potential energy surface for the reaction of the 2-thienylmethyl radical with the HO(2) radical has been examined. Seventeen product channels corresponding to either addition/elimination or direct hydrogen abstraction have been characterized for the first time. Direct hydrogen abstract from HO(2) proceeds via a weakly bound van der Waals complex, which leads to 2-methylthiophene, 2-methylene-2,3-dihydrothiophene, or 2-methylene-2,5-dihydrothiophene depending upon the 2-thienylmethyl radical reaction site. The addition pathway for the two radical reactants is barrierless with the formation of three adducts, as distinguished by HO(2) reaction at three different sites on the 2-thienylmethyl radical. The addition is exothermic by 37-55 kcal mol(-1) relative to the entrance channel, and these excess energies are available to promote further decomposition or rearrangement of the adducts, leading to nascent products such as H, OH, H(2)O, and CH(2)O. The reaction surfaces are characterized by relatively low barriers (most lower than 10 kcal mol(-1)). Upon the basis of a careful analysis of the overall barrier heights and reaction exothermicities, the formations of O(2), OH, and H(2)O are likely to be important pathways in the radical recombination reactions of 2-thienylmethyl + HO(2).     

Insights into the metathesis reaction involving M-M,C-C,and M-C triple bonds from computations employing density functional theory on model compounds M2(OH)6 and M2(SH)6, where M = Mo and W

Calculations employing density functional theory (Gaussian 98, B3LYP, LANL2DZ, 6-31G) have been undertaken to interrogate the factors influencing the metathesis reaction involving M-M, C-C, and M-C triple bonds for the model compounds M(2)(EH)(6), M(2)(EH)(6)(mu-C(2)H(2)), and [(HE)(3)M(tbd1;CH)](2), where M = Mo, W and E = O, S. Whereas in all cases the ethyne adducts are predicted to be enthalpically favored in the reactions between M(2)(EH)(6) compounds and ethyne, only when M = W and E = O is the alkylidyne product [(HO)(3)W(tbd1;CH)](2) predicted to be more stable than the alkyne adduct. For the reaction M(2)(EH)(6)(mu-C(2)H(2)) --> [(HE)(3)M(tbd1;CH)](2), the deltaG degrees values (kcal mol(-)(1)) are -6 (M = W, E = O), +5 (M = Mo, E = O), +18 (M = W, E = S), and +21 (M = Mo, E = S) and the free energies of activation are calculated to be deltaG() = +19 kcal mol(-)(1) (M = W, E = O) and +34 kcal mol(-)(1) (M = Mo, E = O), where the transition state involves an asymmetric bridged structure M(2)(OH)(4)(mu-OH)(2)(CH)(mu-CH) in which the C-C bond has broken; C.C = 1.89 and 1.98 A for W and Mo, respectively. These results are discussed in terms of the experimental observations of the reactions involving ethyne and the symmetrically substituted alkynes (RCCR, where R = Me, Et) with M(2)(O(t)()Bu)(6) and M(2)(O(t)()Bu)(2)(S(t)()Bu)(4) compounds, where M = Mo, W.     

Theoretical study on the mechanism and kinetics for the self-reaction of C2H5O2 radicals

Oxygen-to-oxygen coupling, direct H-abstraction and oxygen-to-(α)carbon nucleophilic substitution processes have been investigated for both the singlet and triplet self-reaction of C(2)H(5)O(2) radicals at the CCSD(T)/cc-pVDZ//B3LYP/6-311G(2d,2p) level to evaluate the reaction mechanisms, possible products and rate constants. The calculated results show that the title reaction mainly occurs through the singlet oxygen-to-oxygen coupling mechanism with the formation of entrance tetroxide intermediates, and the most dominant product is C(2)H(5)O + HO(2) + CH(3)CHO (P5) generated in channel R5. Beginning from the radical products of P5 (C(2)H(5)O, HO(2)) and reactant (C(2)H(5)O(2)), five secondary reactions HO(2) + HO(2) (a), HO(2) + C(2)H(5)O (b), C(2)H(5)O + C(2)H(5)O (c), HO(2) + C(2)H(5)O(2) (d), and C(2)H(5)O + C(2)H(5)O(2) (e) mainly proceed on the triplet potential energy surface. Among these reactions, (a), (b), and (d) are kinetically favorable because of lower barrier heights. The calculated rate constants of channel R5 between 200 and 295 K are almost independent of the temperature, which is in agreement with the experimental report. With regard to the final products distribution, CH(3)CHO, C(2)H(5)OH, C(2)H(5)OOH, H(2)O(2), and (3)O(2) are predicted to be major, whereas C(2)H(5)OOC(2)H(5) should be in minor amount.     

A systematic computational study of the reactions of HO2 with RO2: the HO2 + C2H5O2 reaction

The reaction of HO2 with C2H5O2 has been studied using the density functional theory (B3LYP) and the coupled-cluster theory [CCSD(T)]. The reaction proceeds on the triplet potential energy surface via hydrogen abstraction to form ethyl hydroperoxide and oxygen. On the singlet potential energy surface, the addition-elimination mechanism is revealed. Variational transition state theory is used to calculate the temperature-dependent rate constants in the range 200-1000 K. At low temperatures (e.g., below 300 K), the reaction takes place predominantly on the triplet surface. The calculated low-temperature rate constants are in good agreement with the experimental data. As the temperature increases, the singlet reaction mechanism plays more and more important role, with the formation of OH radical predominantly. The isotope effect of the reaction (DO2 + C2D5O2 vs HO2 + C2H5O2) is negligible. In addition, the triplet abstraction energetic routes for the reactions of HO2 with 11 alkylperoxy radicals (CnHmO2) are studied. It is shown that the room-temperature rate constants have good linear correlation with the activation energies for the hydrogen abstraction.