Time-resolved study on the reactions of organic selenides with hydroxyl and oxide radicals, hydrated electrons, and H-atoms in aqueous solution, and DFT calculations of transients in comparison with sulfur analogues.

A complementary experimental and quantum chemical study has been undertaken on the reactivity, formation and properties of transients generated in the reaction of selected organic selenides with hydroxyl radicals, oxide radical ions, hydrated electrons and hydrogen atoms in aqueous solution. A detailed study of the OH and O (-) reactions with Me(2)Se revealed the formation of the respective adduct-radicals as precursors of (Me(2)Se thereforeSeMe(2))(+) radical cations. In case of the neutral adduct radical Me(2)Se (OH) the conversion into the three-electron bonded dimer species proceeds, in part, via the molecular (Me(2)Se thereforeOH(2))(+) radical cation. Absolute rate constants have been determined for all the underlying processes. The respective reactions with hydrated electrons and hydrogen atoms indicate that selenides exhibit a higher reactivity towards redox-active species than sulfides. A most interesting finding is that the reaction of Me(2)Se with H atoms is faster (k = 4.1 x 10(9) M(-1) s(-1)) than the reduction by hydrated electrons (k = 2.1 x 10(8) M(-1) s(-1)), precluding an electron transfer as mechanistic background. The rationale is rather an effective dissociative attack of the hydrogen atom on the selenium. Both, the e(aq)(-)- and H -induced reductions of Me(2)Se and Me(2)S lead, under cleavage of CH(3) radicals, to the direct formation of selenol and thiol, respectively. Complementary quantum chemical studies, performed with Density Functional Theory (DFT) BHandHLYP methods, confirm this mechanism. They also reveal a generally higher thermodynamic stability of the Se-centered radicals relative to the S-centered ones, e.g., for the molecular radical anions (Me(2)Se) (-) (DeltaH-27 kJ mol(-1)) and (Me(2)S) (-) (DeltaH-16 kJ mol(-1)). Despite of these stabilization energies the calculations indicate an instantaneous Se/S-CH(3) bond lengthening in the respective molecular radical anions. The same applies for the reaction of Me(2)S and Me(2)Se with H atoms. Here the calculations indicate, in fact, no thermodynamic stability of a tentative H-adduct which, therefore, is only a fictional transition state in the H -induced CH(3)-displacement process.

Formation of a sandwich-structure assisted, relatively long-lived sulfur-centered three-electron bonded radical anion in the reduction of a bis(1-substituted-uracilyl) disulfide in aqueous solution.

The one-electron reduction of bis[1-(2',3',5'-tri-O-acetylribosyl)uracil-4-yl] disulfide, initiated by hydrated electrons in a radiation chemical study, has been shown to yield 1-(2',3',5'-tri-O-acetylribosyl)-4-thiouracil as a stable molecular product. The reduction reaction leads, in the first instance, to a transient, albeit remarkably stable disulfide radical anion. This is characterized by a 2-center-3-electron bond with two bonding sigma-electrons and an antibonding sigma*-electron in the sulfur-sulfur bridge, (-S therefore S-)(-). It receives its stability from a sandwich-structure with the two uracilyl moieties facing each other (possibly further assisted by the 2',3',5'-tri-O-acetylribosyl substituents). A considerable lengthening of the original disulfide bridge from 2.02 to 2.73 A in the radical anion seems to facilitate the interaction of the heterocycles and leads to a gain in stabilization energy of 24 and 33 kcal/mol (100 and 140 kJ/mol) as evaluated by UMP2/cc-pVTZ and UMP2/cc-pVDZ calculations, respectively. The (-S therefore S-)(-) bonded radical anion shows a broad optical absorption band with lambdamax=450 nm, epsilonmax=6000 M(-1) cm(-1), and a half-width of 1.0 eV. It exists in equilibrium with the conjugated 1-(2',3',5'-tri- O-acetylribosyl)uracil-4-yl thiyl radical -S(*), and the corresponding thiolate, -S(-). The rate determining step for the disappearance of the disulfide radical anion appears to be protonation of both the radical anion and the free thiolate by reaction with H(+)aq. Absolute rate constants have been measured for these protonation processes, for the formation of the stable thiouridine product, and for the electron transfer from the disulfide radical anion to molecular oxygen. With the (-S therefore S-)(-) <--> -S(*) + -S(-) equilibrium lying very much on the left-hand side, the reduced disulfide system exhibits predominantly reducing properties whereas any oxidizing property of the conjugated thiyl radical has only little if any chance to materialize. Besides attaching directly to the disulfide bridge, the hydrated electrons react also, with about equal efficiency, with the uracil moiety of the investigated compound. This leads to a structurally totally different and electronically distinguishable species than that with the reduced disulfide bridge. In particular, there is no face-to-face interaction between the two heterocyclic moieties and no increased electron density in the S-S bond. The C-centered radicals resulting from the reduction of the uracil and possibly also generated from the ribosyl moieties initiate further cleavage of the S-S bond and thus contribute to the formation of thiouridine. The overall yield of the latter, as determined from steady-state gamma-radiolysis, indicates a small chain process (G=1.54 micromol/J). Possible mechanisms are discussed.

Reactions of halogenated hydroperoxides and peroxyl and alkoxyl radicals from isoflurane in aqueous solution.

Model systems, based on aqueous solutions containing isoflurane (CHF(2)OCHClCF(3)) as an example, have been studied in the presence and absence of methionine (MetS) to evaluate reactive fates of halogenated hydroperoxides and peroxyl and alkoxyl radicals. Primary peroxyl radicals, CHF(2)OCH(OO*)CF(3), generated upon 1-e-reduction of isoflurane react quantitatively with MetS via an overall two-electron oxidation mechanism to the corresponding sulfoxide (MetSO). This reaction is accompanied by the formation of oxyl radicals CHF(2)OCH(O*)CF(3) that quantitatively rearrange by a 1,2-hydrogen shift to CHF(2)OC*(OH)CF(3). According to quantum-chemical calculations, this reaction is exothermic (DeltaH = -5.1 kcal/mol) in contrast to other potentially possible pathways. These rearranged CHF(2)OC*(OH)CF(3) radicals react further via either of two pathways: (i) direct addition of oxygen or (ii) deprotonation followed by fluoride elimination resulting in CHF(2)OC(O)CF(2)*. Route i yields the corresponding CHF(2)OC(OO*)(OH)CF(3) peroxyl radicals, which eliminate H+/O(2)*-. The resulting ester, CHF(2)OC(O)CF(3), hydrolyzes further, accounting for the formation of HF, trifluoroacetic acid, and formic acid with a contribution of 45% and 80% in air- and oxygen-saturated solutions, respectively. A competitive pathway (ii) involves the reactions of the secondary peroxyl radicals, CHF(2)OC(O)CF(2)OO*. The two more stable of the three above mentioned peroxyl radicals can be distinguished through their reaction with MetS. Although the primary CHF(2)OCH(OO*)CF(3) oxidizes MetS to MetSO in a 2-e step, the majority of the secondarily formed CHF(2)OC(O)CF(2)OO* reacts with MetS via a 1-e transfer mechanism, yielding CHF(2)OC(O)CF(2)OO-, which eventually suffers a total breakup into CHF(2)O- + CO(2) + CF(2)O. Quantum-chemical calculations show that this reaction is highly exothermic (DeltaH = -81 kcal/mol). In air-saturated solution this pathway accounts for about 35% of the overall isoflurane degradation. Minor products (10% each), namely, oxalic acid and carbon monoxide originate from oxyl radicals, CHF(2)OC(O)CF(2)O* and CHF(2)OCH(O*)CF(3). An isoflurane-derived hydroperoxide CHF(2)OCH(OOH)CF(3) in high yield was generated in radiolysis of air-saturated solutions containing isoflurane and formate either via a H-atom abstraction from formate by the isoflurane-derived peroxyl radicals or by their cross-termination reaction with superoxide O(2)*-. CHF(2)OCH(OOH)CF(3), is an unstable intermediate whose multistep hydrolysis is giving H(2)O(2) + 2HF + HC(O)OH + CF(3)CH(OH)(2). In the absence of MetS, about 55% of CHF(2)OCH(OO*)CF(3) undergo termination via the Russell mechanism and 27% are involved in cross-termination with superoxide (O(2)*-) and peroxyl radicals derived from t-BuOH (used to scavenge *OH radicals). The remaining 18% of the primary peroxyl radicals undergo termination via formation of alkoxyl radicals, CHF(2)OCH(O*)CF(3).

One-electron reduction of methanesulfonyl chloride. The fate of MeSO2Cl(.)(-) and MeSO2(.) intermediates in oxygenated solutions and their role in the cis-trans isomerization of mono-unsaturated fatty acids.

The one-electron reduction of methanesulfonyl chloride (MeSO2Cl) leads, in the first instance, to an electron adduct MeSO2Cl(.)(-) which lives long enough for direct detection and decays into sulfonyl radicals MeSO2(.) and Cl(-), with k = 1.5 x 10(6) s(-1). Both, MeSO2Cl(.)(-) and MeSO2(.) showed a similar absorption in the UV with lambdamax of 320 nm. In the presence of oxygen, MeSO2Cl(.)(-) transfers an electron to O(2) and establishes an equilibrium with superoxide. The rate constant for the forward reaction was measured to 4.1 x 10(9) M(-1) s(-1), while for the back reaction only an interval of 1.7 x 10(5) to 1.7 x 10(6) M(-1) s(-1) could be estimated, with a somewhat higher degree of confidence for the lower value. This corresponds to an equilibrium constant in the range of 2.4 x 10(3) to 2.4 x 10(4). With reference to E degrees (O2/O2(.)(-)) = -155 mV, the redox potential of the sulfonyl chloride couple, E degrees (MeSO2Cl/MeSO2Cl(.)(-)), thus results between being equal to -355 and -414 mV (vs NHE). MeSO2Cl(.)(-) reduces (besides O2) 4-nitroacetophenone. The underlying electron transfer took place with k = 1.5 x 10(9) M(-1) s(-1), corroborating an E degrees for the sulfonyl chloride couple significantly exceeding the above listed lower value. The MeSO2(.) radical added to oxygen with a rate constant of 1.1 x 10(9) M(-1) s(-1). Re-dissociation of O2 from MeSO2OO(.) occurred only very slowly, if at all, that is, with k << 10(5) s(-1). MeSO2(.) radicals can act as the catalyst for the cis-trans isomerization of several Z- and E-mono-unsaturated fatty acid methyl esters in homogeneous solution. The effectiveness of the isomerization processes has been addressed, and in the presence of oxygen the isomerization is completely suppressed.

Transients in the oxidative and H-atom-induced degradation of 1,3,5-trithiane. Time-resolved studies in aqueous solution.

The (*)OH-induced oxidation of 1,3,5-trithiacyclohexane (1) in aqueous solution was studied by means of pulse radiolysis with optical and conductivity detection. This oxidation leads, via a short-lived (*)OH radical adduct (<1 micros), to the radical cation 1(*+) showing a broad absorption with lambda(max) equal to 610 nm. A defined pathway of the decay of 1(*+) is proton elimination. It occurs with k = (2.2 +/- 0.2) x 10(4) s(-1) and yields the cyclic C-centered radical 1(-H)(*). The latter radical decays via ring opening (beta-scission) with an estimated rate constant of about 10(5) s(-1). A distinct, immediate product (formed with the same rate constant) is characterized by a narrow absorption band with lambda(max) = 310 nm and is attributed to the presence of a dithioester function. The formation of the 310 nm absorption can be suppressed in the presence of oxygen, the rationale for this being a reaction of the C-centered cyclic radical 1(-H)(*) with O(2). The disappearance of the 310 nm band (with a rate constant of 900 s(-1)) is associated with the hydrolysis of the dithioester functionality. A further aspect of this study deals with the reaction of H(*) atoms with 1 which yields a strongly absorbing, three-electron-bonded 2sigma/1sigma* radical cation [1(S therefore S)-H](+) (lambda(max) = 400 nm). Its formation is based on an addition of H(*) to one of the sulfur atoms, followed by beta-scission, intramolecular sulfur-sulfur coupling (constituting a ring contraction), and further stabilization of the S therefore S bond thus formed by protonation. [1(S therefore S)-H](+) decays with a first-order rate constant of about 10(4) s(-1). Its formation can be suppressed by the addition of oxygen which scavenges the H(*) atoms prior to their reaction with 1. Complementary time-resolved conductivity experiments have provided information on the quantification of the 1(*+) radical cation yield, the cationic longer-lived follow-up species, extinction coefficients, and kinetics concerning deprotonation processes as well as further reaction steps after hydrolysis of the transient dithioesters. The results are also discussed in the light of previous photochemical studies.