Kinetics and Mechanisms of Hydrothermal Dehydration of Cyclic 1,2- and 1,4-Diols.

Hydrothermal dehydration is an attractive method for deoxygenation and upgrading of biofuels because it requires no reagents or catalysts other than superheated water. Although mono-alcohols cleanly deoxygenate via dehydration under many conditions, polyols such as those derived from saccharides and related structures are known to be recalcitrant with respect to dehydration. Here, we describe detailed mechanistic and kinetic studies of hydrothermal dehydration of 1,2- and 1,4-cyclohexanediols as model compounds to investigate how interactions between the hydroxyls can control the reaction. The diols generally dehydrate more slowly and have more complex reaction pathways than simple cyclohexanol. Although hydrogen bonding between hydroxyls is an important feature of the diol reactions, hydrogen bonding on its own does not explain the reduced reactivity. Rather, it is the way that hydrogen bonding influences the balance between the E1 and E2 elimination mechanisms. We also describe the reaction pathways and follow-up secondary reactions for the slower-dehydrating diols.

Understanding the Solvent Contribution to Chemical Reaction Barriers.

Absolute rate theories attempt to predict the rate constants of reactions from basic principles and independent data. For the contribution of solvent to a reaction rate constant, this requires connecting absolute rate data to fundamental solvent properties such as dielectric constant and refractive index. We have explored this connection for the unimolecular fragmentation reaction of a pinacol radical cation. The rate constants for fragmentation were measured as a function of temperature in 12 different solvents with dielectric constants from 4.7 to 36.2, and the free energies of activation for bond fragmentation in each solvent determined using transition state theory. Using the solvent effects on electron-transfer reactions as a starting point, Marcus theory was used to model the solvent effect on the reaction activation energies. The solvent contribution to both the activation free energy and the overall reaction energy is best described using the Born model rather than the Pekar solvation model. The solvent reorganization energies for bond fragmentation are substantially larger than solvent reorganization energies for electron transfer, presumably because of the requirement to translate the solvent molecules in the course of bond breaking.

Reversible Electrochemical Trapping of Carbon Dioxide Using 4,4'-Bipyridine That Does Not Require Thermal Activation.

Sequestering carbon dioxide emissions by the trap and release of CO2 via thermally activated chemical reactions has proven problematic because of the energetic requirements of the release reactions. Here we demonstrate trap and release of carbon dioxide using electrochemical activation, where the reactions in both directions are exergonic and proceed rapidly with low activation barriers. One-electron reduction of 4,4'-bipyridine forms the radical anion, which undergoes rapid covalent bond formation with carbon dioxide to form an adduct. One-electron oxidation of this adduct releases the bipyridine and carbon dioxide. Reversible trap and release of carbon dioxide over multiple cycles is demonstrated in solution at room temperature, and without the requirement for thermal activation.

Hydrothermal photochemistry as a mechanistic tool in organic geochemistry: the chemistry of dibenzyl ketone.

Hydrothermal organic transformations under geochemically relevant conditions can result in complex product mixtures that form via multiple reaction pathways. The hydrothermal decomposition reactions of the model ketone dibenzyl ketone form a mixture of reduction, dehydration, fragmentation, and coupling products that suggest simultaneous and competitive radical and ionic reaction pathways. Here we show how Norrish Type I photocleavage of dibenzyl ketone can be used to independently generate the benzyl radicals previously proposed as the primary intermediates for the pure hydrothermal reaction. Under hydrothermal conditions, the benzyl radicals undergo hydrogen atom abstraction from dibenzyl ketone and para-coupling reactions that are not observed under ambient conditions. The photochemical method allows the primary radical coupling products to be identified, and because these products are generated rapidly, the method also allows the kinetics of the subsequent dehydration and Paal-Knorr cyclization reactions to be measured. In this way, the radical and ionic thermal and hydrothermal reaction pathways can be studied separately.

N-alkoxyheterocycles as irreversible photooxidants.

Irreversible photooxidation based on N-O bond fragmentation is demonstrated for N-methoxyheterocycles in both the singlet and triplet excited state manifolds. The energetic requirements for bond fragmentation are studied in detail. Bond fragmentation in the excited singlet manifold is possible for ππ* singlet states with energies significantly larger than the N-O bond dissociation energy of ca 55 kcal mol(-1). For the nπ* triplet states, N-O bond fragmentation does not occur in the excited state for orbital overlap and energetic reasons. Irreversible photooxidation occurs in the singlet states by bond fragmentation followed by electron transfer. Irreversible photooxidation occurs in the triplet states via bimolecular electron transfer to the donor followed by bond fragmentation. Using these two sensitization schemes, donors can be irreversibly oxidized with oxidation potentials ranging from ca 1.6-2.2 V vs SCE. The corresponding N-ethylheterocycles are characterized as conventional reversible photooxidants in their triplet states. The utility of these sensitizers is demonstrated by irreversibly generating the guanosine radical cation in buffered aqueous solution.

Neighboring pyrrolidine amide participation in thioether oxidation. Methionine as a "hopping" site.

Methionine residues have been shown to function as efficient "hopping" sites in long-range electron transfer in model polyprolyl peptides. We suggest that a key to this ability of methionine is stabilization of the transient sulfur radical cation by neighboring proline amide participation. That is, in a model system a neighboring pyrrolidine amide lowers the oxidation potential of the thioether by over 0.5 V by formation of a two-center three-electron SO bond.

Electrochemical and chemical oxidation of dithia-, diselena-, ditellura-, selenathia-, and tellurathiamesocycles and stability of the oxidized species.

The diverse electrochemical and chemical oxidations of dichalcogena-mesocycles are analyzed, broadening our understanding of the chemistry of the corresponding radical cations and dications. 1,5-Diselenocane and 1,5-ditellurocane undergo reversible two-electron oxidation with inverted potentials analogous to 1,5-dithiocane. On the other hand, 1,5-selenathiocane and 1,5-tellurathiocane undergo one-electron oxidative dimerization. The X-ray crystal structures of the Se-Se dimer of the 1,5-selenathiocane one-electron oxidized product and the monomeric two-electron oxidized product (dication) of 1,5-tellurathiocane are reported. 1,5-Dithiocanes and 1,5-diselenocanes with group 14 atoms as ring members undergo irreversible oxidation, unlike the reversible two-electron oxidation of the corresponding silicon-containing 1,5-ditellurocanes. These results demonstrate the chemical consequences of the dication stabilities Te(+)-Te(+) > Se(+)-Se(+) > S(+)-S(+), as well as Se(+)-Se(+) > Se(+)-S(+) and Te(+)-Te(+) > Te(+)-S(+).

Neighboring amide participation in thioether oxidation: relevance to biological oxidation.

To investigate neighboring amide participation in thioether oxidation, which may be relevant to brain oxidative stress accompanying beta-amyloid peptide aggregation, conformationally constrained methylthionorbornyl derivatives with amido moieties were synthesized and characterized, including an X-ray crystallographic study of one of them. Electrochemical oxidation of these compounds, studied by cyclic voltammetry, revealed that their oxidation peak potentials were less positive for those compounds in which neighboring group participation was geometrically possible. Pulse radiolysis studies provided evidence for bond formation between the amide moiety and sulfur on one-electron oxidation in cases where the moieties are juxtaposed. Furthermore, molecular constraints in spiro analogues revealed that S-O bonds are formed on one-electron oxidation. DFT calculations suggest that isomeric sigma*(SO) radicals are formed in these systems.

Interaction of C-Si, C-Sn, and Si-Si sigma-bonds with chalcogen lone pairs.

The ability of neighboring C-Si, C-Sn, and Si-Si groups in conformationally constrained cyclic molecules to reduce the lowest ionization energies of sulfur, selenium, and tellurium compounds has been determined by charge-transfer spectroscopy of complexes with tetracyanoethylene. For selected compounds, ionization energies were determined by gas-phase photoelectron spectroscopy. The lowest ionization energies measured by photoelectron spectroscopy, with one exception, correlate with the charge-transfer spectroscopic data. In addition, theoretical analysis has provided insight into the photoelectron spectra and the geometry-dependent interaction between C-Si or C-Sn bonds and chalcogen lone pairs. Substantial lowering of ionization energies is found which is anticipated to have important consequences in the chemistry of these and related species.

The Si-Si effect on ionization of beta-disilanyl sulfides and selenides.

The ionization energies of conformationally constrained, newly synthesized beta-disilanyl sulfides and selenides were determined by photoelectron spectroscopy. These ionization energies reflect substantial (0.53-0.75 eV) orbital destabilizations. The basis for these destabilizations was investigated by theoretical calculations, which reveal geometry-dependent interaction between sulfur or selenium lone pair orbitals and sigma-orbitals, especially Si-Si sigma-orbitals. These results presage facile redox chemistry for these compounds and significantly extend the concept of sigma-stabilization of electron-deficient centers.

Kinetics of proton transfer from cationic carbon acids in water and aqueous DMSO. Effect of activating groups and solvent on intrinsic rate constants.

[reaction: see text] Acidity constants and rates of reversible deprotonation of acetonyltriphenylphosphonium ion (1H+), phenacyltriphenylphosphonium ion (2H+), N-methyl-4-phenacylpyridinium ion (3H+), and N-methyl-4-(phenylsulfonylmethyl)pyridinium ion (4H+) by amines in water, 50% DMSO-50% water (v/v), and 90% DMSO-10% water (v/v) have been determined. From the respective Brønsted plots, log k(o) values for the intrinsic rate constants of the various proton transfers were obtained. Solvent transfer activity coefficients of the carbon acids and their respective conjugate bases were also determined which helped in understanding how the pKa values and intrinsic rate constants depend on the solvent. Some of the main conclusions are as follows: (1) The pK(a) values of 1H+, 2H+, and 3H+ are significantly higher than that of 4H+ because of a stronger resonance stabilization of the corresponding conjugate bases 1, 2 and 3, respectively. (2) The electronic effects of the PPh3+ and the N-methyl-4-pyridylium group are similar but the mix between inductive and resonance effect is different. (3) All four acids become more acidic upon addition of DMSO to the solvent. In all cases, the main factor is the stronger solvation of H3O+ in DMSO; for 1H+, 2H+, and 3H+ but not 4H+ this factor is significantly attenuated by stronger solvation of the carbon acid in DMSO. (4) The intrinsic rate constants for proton transfer are relatively high for all four carbon acids and show little solvent dependence; this contrasts with nitroalkanes which have much lower intrinsic rate constants and show a strong solvent dependence. These results can be understood by a detailed analysis of the interplay between inductive, resonance, and solvation effects.

Synthesis, gas-phase photoelectron spectroscopic, and theoretical studies of stannylated dinuclear iron dithiolates.

Stannylated dinuclear iron dithiolates (mu-SSnMe(2)CH(2)S)[Fe(CO)(3)](2), (mu-SCH(2)SnMe(2)CH(2)S) [Fe(CO)(3)](2), and (mu-SCH(2)SnMe(3))(2)[Fe(CO)(3)](2), which are structurally similar to the active site of iron-only hydrogenase, were synthesized and studied by gas-phase photoelectron spectroscopy. The orbital origins of ionizations were assigned by comparison of He I and He II photoelectron spectra and with the aid of hybrid density functional electronic structure calculations. Stannylation lowers the ionization energy of sulfur lone pair orbitals in these systems owing to a geometry-dependent interaction. The Fe-Fe sigma bond, which is the HOMO in all these systems, is also substantially destabilized by stannylation due to a previously unrecognized geometry-dependent interaction between axial sulfur lone pair orbitals and the Fe-Fe sigma bond. Since cleaving the Fe-Fe sigma bond is a key step in the mechanism of action of iron-only hydrogenase, these newly recognized geometry-dependent interactions may be utilized in designing biologically inspired hydrogenase catalysts.

Density functional theory predicts the barriers for radical fragmentation in solution.

[reaction: see text] N-Methoxypyridyl radicals formed by one-electron reduction of the corresponding cationic heterocycles undergo N-O bond cleavage. Experimental activation free energies for a series of these bond fragmentations are compared to corresponding barriers determined from electronic structure calculations. The DFT barriers agree well with those from experiment, being smaller than the latter values by an average value of ca. 1 kcal/mol, for rate constants varying over almost 3 orders of magnitude, or within ca. 3 kcal/mol over 8 orders of magnitude of rate constant. For a model compound, the B3PW91/6-31+G hybrid density functional method is also found to be in good agreement with the MCSCF-MRMP2 method. One of the reactions is found by DFT to have no minimum for the reactant radical, consistent with a truly barrierless reaction.

A quantitative curve-crossing model for radical fragmentation.

The kinetics of bond fragmentation for a series of N-methoxypyridyl radicals are analyzed in terms of a simple curve-crossing model that includes bond stretching and bond bending coordinates. The model accurately reproduces the reaction surfaces calculated using density functional theory (DFT) and also the experimental reaction energy barriers. The reactions proceed on the ground state surface by avoidance of a conical intersection, which is clearly illustrated by the model. A value for the electronic coupling matrix element responsible for splitting the upper and lower surfaces of 0.9 eV is obtained. The model illustrates the molecular features that allow barrierless fragmentation from a formally pi radical.

Barrierless electron transfer bond fragmentation reactions.

The ultrafast N-O bond fragmentation in a series of N-methoxypyridyl radicals, formed by one-electron reduction of the corresponding N-methoxypyridiniums, has been investigated as potentially barrierless electron-transfer-initiated chemical reactions. A model for the reaction involving the electronic and geometric factors that control the shape of the potential energy surface for the reaction is described. On the basis of this model, molecular structural features appropriate for ultrafast reactivity are proposed. Femtosecond kinetic measurements on these reactions are consistent with a kinetic definition of an essentially barrierless reaction, i.e., that the lifetime of the radical is a few vibrational periods of the fragmenting bond, for the p-methoxy-N-methoxypyridyl radical.

Synthesis, electrochemistry, and gas-phase photoelectron spectroscopic and theoretical studies of 3,6-bis(perfluoroalkyl)-1,2-dithiins.

3,6-bis(trifluoromethyl)- and 3,6-bis(pentafluoroethyl)-1,2-dithiin (1a,b), the first known perfluoroalkyl-substituted 1,2-dithiins, were synthesized from (Z,Z)-1,4-bis(tert-butylthio)-1,3-butadiene (2) to evaluate the effects of electron-withdrawing groups on the ionization and oxidation potentials of 1,2-dithiins. Analysis of the photoelectron spectra of 1a and 1b provided a basis for assigning orbital compositions. Ab initio calculations on these compounds showed that they adopt a twist geometry as does 1,2-dithiin (1c) itself. Cyclic voltammetric studies on 1a and 1b revealed a reversible oxidation followed by an irreversible oxidation at much more positive potentials than for 1,2-dithiin and 3,6-dimethyl-1,2-dithiin (1d). The oxidation potentials determined electrochemically do not correlate with the ionization potentials determined by photoelectron spectroscopy. This result supports the previously advanced hypothesis that there is a geometry change on electrochemical oxidation leading to a planar radical cation.

Kinetics of reductive N-O bond fragmentation: the role of a conical intersection.

N-alkoxyheterocycles can act as powerful one-electron acceptors in photochemical electron-transfer reactions. One-electron reduction of these species results in formation of a radical that undergoes N-O bond fragmentation to form an alkoxy radical and a neutral heterocycle. The kinetics of this N-O bond fragmentation reaction have been determined for a series of radicals with varying substituents and extents of delocalization. Rate constants varying over 7 orders of magnitude are obtained. A reaction potential energy surface is described that involves avoidance of a conical intersection. A molecular basis for the variation of the reaction rate constant with radical structure is given in terms of the relationship between the energies of the important molecular orbitals and the reaction potential energy surface. Ab initio and density functional electronic structure calculations provide support for the proposed reaction energy surface.