A large entropic term due to water rearrangement is concomitant with the photoproduction of anionic free-base porphyrin triplet states in aqueous solutions.

The enthalpy change, DeltaTH, and volume change, DeltaTV, associated with triplet state formation upon excitation of free-base meso-tetra-(4-sulfonatophenyl)porphyrin, TSPP4-, its Zn derivative, ZnTSPP4-, and meso-tetra-(4-carboxyphenyl)porphyrin, TCPP4-, were obtained in aqueous solutions by the application of laser-induced optoacoustics spectroscopy in the presence of phosphate salts of various monovalent cations (Li+, Na+, K+, NH4+ and Cs+). A linear correlation was found between DeltaTH and DeltaTV at different phosphate concentrations for the free-base porphyrins. The intercepts (132 +/- 8 kJ mol(-1) for TSPP4- and 164 +/- 23 kJ mol(-1) for TCPP4-) of these plots correspond to the respective value of the triplet energy content obtained from phosphorescence at 77 K (140 and 149 kJ mol(-1)). This suggests that DeltaTG for the triplet state formation is independent of the medium and an enthalpy-entropy compensation is responsible for the much smaller and salt-dependent DeltaTH values obtained at room temperature. The Gibbs energy for triplet state formation of the free-base porphyrins at room temperature is thus mainly determined by the entropic term due to solvent rearrangement. The DeltaTH values for 3ZnTSPP4- at different buffer concentrations and different cations are all between 130 and 150 kJ mol(-1), close to the triplet energy obtained from phosphorescence (E(T) = 155 kJ mol(-1)). The solvent structure and the nature of the counterion have a negligible influence on the 3ZnTSPP4-formation due to the blockage of the electron pairs on the central N atoms. Thus, the small DeltaTV value should be due to intrinsic bond changes upon 3ZnTSPP4- formation and no correlation between DeltaTH and DeltaTV should be expected in this case. The enthalpy change determines the Gibbs energy for 3ZnTSPP4-formation at room temperature.

Kinetic and theoretical studies on the mechanism of intramolecular catalysis in phenyl ester hydrolysis.

The kinetic study of the hydrolysis reaction of Z-substituted phenyl hydrogen maleates (Z = H, m-CH3, p-CH3, m-Cl, p-Cl and m-CN) was carried out in aqueous solution, and the results were complemented with theoretical studies. Under some experimental conditions, two kinetic processes were observed. One of them was ascribed to maleic anhydride formation and the other to the anhydride hydrolysis. The Brönsted-type plot for the leaving-group dependence was linear with slope beta(lg) = -1. The experimental results are consistent with a mechanism that involves significant bond breaking in the rate-limiting transition state (alpha(lg) = 0.64). Theoretical results for the reaction in the gas phase showed an excellent Brönsted-type dependence with a beta(lg) of -1.03. A tetrahedral intermediate (TI) could not be found through DFT gas-phase studies (B3LYP/6-311+G*). Calculations carried out within a continuous solvation model or with discrete water molecules failed to find a stable TI. With both models, a flat region on the potential-energy surface is found and a tight optimization of the structures led back to starting materials. The theoretical results do not discard the possible existence of an unstable intermediate on the free-energy surface, but the analysis of the whole body of results compared with other acyl transfer reactions lead us to suggest that an enforced concerted mechanism is the most appropriate to describe these reactions.

Photoinduced electron transfer from tetrasulfonated porphyrin to benzoquinone revisited. The structural volume-normalized entropy change correlates with marcus reorganization energy.

Time-resolved laser-induced optoacoustic spectroscopy was used for the determination of the enthalpy, DeltaTH, and structural volume changes, DeltaTV, concomitant with triplet state formation upon excitation of meso-tetrakis(4-sulfonatophenyl)porphyrin, TSPP(4-), as well as with the triplet state electron-transfer (ET) quenching by benzoquinone, BQ (DeltaRH and DeltaRV). The values of DeltaTH and DeltaTV for (3)TSPP(4-) formation in the presence of different cations (Li+, Na+, K+, NH4+, and Cs+) correlated with each other and afforded a value of DeltaTG = 140 +/- 20 kJ mol(-1), equal to the value of E+ at 77 K, but much larger than the DeltaTH values in solution at room temperature, due to the large entropic factor in solution. The influence of the cations on DeltaTH and DeltaTV (a contraction ranging from 5.4 to 3.8 cm3 mol(-1)) is attributed to changing chromophore-water interactions in the ground and triplet states. Upon quenching of 3TSPP(4-) by BQ, the quantum yield of free radical formation, PhiR = 0.66 +/- 0.04, is the same in the solutions of the five cations. The values of DeltaRH and DeltaRV are small and have a large error. The energy level of the free radicals formed is thus very similar to that of 3TSPP(4-). TDeltaRS and X = TDeltaRS/DeltaRV, i.e., the structural volume change-normalized entropy change for free radicals formation, were derived using average values of DeltaRH and DeltaRV together with the calculated DeltaRG degrees . The measured Marcus reorganization energy, lambda, and X fall into the lambda vs X linear dependence we previously found for the radical formation upon ET quenching of triplet flavins (3FMN and 3FAD) by amines and amino acids. Thus, X = TDeltaRS/DeltaRV in aqueous solutions is a property of the particular donor-acceptor pair linearly correlated to the corresponding Marcus reorganization energy. The value of X is much larger than the predicted value applying the electrostriction concepts in view of the noncontinuum nature of the aqueous solutions.

Kinetics and mechanistic study of the reaction of cyclic anhydrides with substituted phenols. Structure-reactivity relationships.

[reaction: see text] The kinetic of the reactions of phthalic and maleic anhydrides with different substituted phenols (Z-PhOH with Z = H, m-CH(3), p-CH(3), m-Cl, p-Cl, and m-CN) were studied in aqueous solution. Two kinetic processes well separated in time were observed. The fast one is attributed to the formation of the aryl ester in equilibrium with the anhydride and allows the determination of the rate of nucleophilic attack of the phenol on the anhydride (k(-)(A)). From the slow kinetic process, the equilibrium constant for this reaction was determined. The Bronsted-type plots for the nucleophilic attack of substituted phenols on the anhydrides were linear with slopes beta(Nuc) of 0.45 and 0.56 for phthalic and maleic anhydride, respectively. The results are consistent with a mechanism involving rate-determining nucleophilic attack and also with a concerted mechanism. The calculated effective charge on the atoms involved in the reactions and the Bronsted beta values are consistent with a mechanism involving a concerted or enforced concerted mechanism where a tetrahedral intermediate with significant lifetime is not formed along the reaction coordinate. The latter mechanism is preferred over the stepwise process.