What a difference a chlorine makes: The remarkable unimolecular ion chemistry of phenyl formate and phenyl chloroformate.

Imaging photoelectron photoion coincidence (iPEPICO) spectroscopy and tandem mass spectrometry were employed to explore the ionisation and dissociative ionisation of phenyl formate (PF) and phenyl chloroformate (PCF). The threshold photoelectron spectra of both compounds are featureless and lack a definitive origin transition, owing to the internal rotation of the formate functional group relative to the benzene ring, active upon ionisation. CBS-QB3 calculations yield ionisation energies of 8.88 and 9.03 eV for PF and PCF, respectively. Ionised PF dissociates by the loss of CO via a transition state composed of a phenoxy cation and HCO moieties. The dissociation of PCF ions involves the competing losses of CO (m/z 128/130), Cl (m/z 121) and CO2 (m/z 112/114), with Cl loss also shown to occur from the second excited state in a non-statistical process. The primary CO- and Cl-loss fragment ions undergo sequential reactions leading to fragment ions at m/z 98 and 77. The mass-analysed ion kinetic energy (MIKE) spectrum of PCF+ showed that the loss of CO2 occurs with a large reverse energy barrier, which is consistent with the computationally derived minimum energy reaction pathway.

The Unimolecular Chemistry of Methyl Chloroformate Ions and Neutrals: A Story of Near-Threshold Decomposition.

The near-threshold dissociation of ionized and neutral methyl chloroformate (CH3COOCl, MCF) was explored with imaging photoelectron photoion coincidence spectroscopy. The threshold photoelectron spectrum (TPES) for MCF was acquired for the first time; the large geometry changes upon ionization of MCF result in a broad, poorly defined TPES. Franck-Condon simulations are consistent with an adiabatic ionization energy (IE) of 10.90 ± 0.05 eV. Ionized MCF dissociates by chlorine atom loss at a measured 0 K appearance energy (AE) of 11.30 ± 0.01 eV. Together with the above IE, this AE suggests a reaction barrier of 0.40 ± 0.05 eV, consistent with the SVECV-f12 computational result of 0.41 eV. At higher internal energies, the loss of CH3O• becomes competitive due to its lower entropy of activation. Pyrolysis of neutral MCF formed the anticipated major products CH3Cl + CO2 (R1) and the minor products HCl + CO + CH2O (R2). The thermal decomposition products were identified by their photoion mass-selected threshold photoelectron spectrum (ms-TPES). Possible reaction pathways were explored computationally to confirm the dominant ones: R1 proceeds by a concerted Cl atom migration via a four-membered transition state in agreement with the mechanism proposed in the literature. R2 is a two-step reaction first yielding 2-oxiranone by HCl loss, which then decomposes to CH2O and CO. Kinetic modeling of the neutral decomposition could simulate the observed reactions only if the vibrational temperature of the MCF was assumed not to cool in the expansion.

Probing the pyrolysis of ethyl formate in the dilute gas phase by synchrotron radiation and theory.

The thermal decomposition of the atmospheric constituent ethyl formate was studied by coupling flash pyrolysis with imaging photoelectron photoion coincidence (iPEPICO) spectroscopy using synchrotron vacuum ultraviolet (VUV) radiation at the Swiss Light Source (SLS). iPEPICO allows photoion mass-selected threshold photoelectron spectra (ms-TPES) to be obtained for pyrolysis products. By threshold photoionization and ion imaging, parent ions of neutral pyrolysis products and dissociative photoionization products could be distinguished, and multiple spectral carriers could be identified in several ms-TPES. The TPES and mass-selected TPES for ethyl formate are reported for the first time and appear to correspond to ionization of the lowest energy conformer having a cis (eclipsed) configuration of the O=C(H)-O-C(H2 )-CH3 and trans (staggered) configuration of the O=C(H)-O-C(H2 )-CH3 dihedral angles. We observed the following ethyl formate pyrolysis products: CH3 CH2 OH, CH3 CHO, C2 H6 , C2 H4 , HC(O)OH, CH2 O, CO2 , and CO, with HC(O)OH and C2 H4 pyrolyzing further, forming CO + H2 O and C2 H2  + H2 . The reaction paths and energetics leading to these products, together with the products of two homolytic bond cleavage reactions, CH3 CH2 O + CHO and CH3 CH2  + HC(O)O, were studied computationally at the M06-2X-GD3/aug-cc-pVTZ and SVECV-f12 levels of theory, complemented by further theoretical methods for comparison. The calculated reaction pathways were used to derive Arrhenius parameters for each reaction. The reaction rate constants and branching ratios are discussed in terms of the residence time and newly suggest carbon monoxide as a competitive primary fragmentation product at high temperatures.

Characterization of Binding Properties of Cr(Phen)3 3+ and Ru(Phen)3 2+ Complexes with Human Lactoferrin.

This work presents research about [Cr(phen)3 ]3+ and [Ru(phen)3 ]2+ interaction with human lactoferrin (HLf), a key carrier protein of ferric cations. The photochemical and photophysical properties of [Cr(phen)3 ]3+ and [Ru(phen)3 ]2+ have been widely studied in the last decades due to their potential use as photosensitizers in photodynamic therapy (PDT). The behavior between the complexes and the protein was studied employing UV-visible absorption, fluorescence emission and circular dichroism spectroscopic techniques. It was found that both complexes bind to HLf with a large binding constant (Kb ): 9.46 × 104 for the chromium complex and 4.16 × 104 for the ruthenium one at 299 K. Thermodynamic parameters were obtained from the Van't Hoff equation. Analyses of entropy (ΔS), enthalpy (ΔH) and free energy changes (ΔG) indicate that these complexes bind to HLf because of entropy-driven processes and electrostatic interactions. According to circular dichroism experiments, no conformational changes have been observed in the secondary and tertiary structure of the protein in the presence of any of the studied complexes. These experimental results suggest that [Cr(phen)3 ]3+ and [Ru(phen)3 ]2+ bind to HLf, indicating that this protein could act as a carrier of these complexes in further applications.

Probing the pyrolysis of methyl formate in the dilute gas phase by synchrotron radiation and theory.

The thermal dissociation of the atmospheric constituent methyl formate was probed by coupling pyrolysis with imaging photoelectron photoion coincidence spectroscopy (iPEPICO) using synchrotron VUV radiation at the Swiss Light Source (SLS). iPEPICO allows threshold photoelectron spectra to be obtained for pyrolysis products, distinguishing isomers and separating ionic and neutral dissociation pathways. In this work, the pyrolysis products of dilute methyl formate, CH3 OC(O)H, were elucidated to be CH3 OH + CO, 2 CH2 O and CH4 + CO2 as in part distinct from the dissociation of the radical cation (CH3 OH+• + CO and CH2 OH+ + HCO). Density functional theory, CCSD(T), and CBS-QB3 calculations were used to describe the experimentally observed reaction mechanisms, and the thermal decomposition kinetics and the competition between the reaction channels are addressed in a statistical model. One result of the theoretical model is that CH2 O formation was predicted to come directly from methyl formate at temperatures below 1200 K, while above 1800 K, it is formed primarily from the thermal decomposition of methanol.

Trifluoroacetic Acid and Trifluoroacetic Anhydride Radical Cations Dissociate near the Ionization Limit.

The threshold photoelectron spectra (TPES) and ion dissociation breakdown curves for trifluoroacetic acid (TFA) and trifluoroacetic anhydride (TFAN) were measured by imaging photoelectron photoion coincidence spectroscopy employing both effusive room-temperature samples and samples introduced in a seeded molecular beam. The fine structure in the breakdown diagram of TFA mirroring the vibrational progression in the TPES suggests that direct ionization to the X̃+ state leads to parent ions with a lower "effective temperature" than nonresonant ionization in between the vibrational progression. Composite W1U, CBS-QB3, CBS-APNO, G3, and G4 calculations yielded an average ionization energy (IE) of 11.69 ± 0.06 eV, consistent with the experimental value of 11.64 ± 0.01 eV, based on Franck-Condon modeling of the TPES. The measured 0 K appearance energies (AE0K) for the reaction forming CO2H+ + CF3 from TFA were 11.92 for effusive data and 11.94 ± 0.01 eV for molecular beam data, consistent with the calculated composite method 0 K reaction energy of 11.95 ± 0.08 eV. Together with the 0 K heats of formation (ΔfH0K) of CO2H+ and CF3, this yields a ΔfH0K of neutral TFA of -1016.6 ± 1.5 kJ mol-1 (-1028.3 ± 1.5 kJ mol-1 at 298 K). TFAN did not exhibit a molecular ion at room-temperature conditions, but a small signal was observed when rovibrationally cold species were probed in a molecular beam. The two observed dissociation channels were CF3C(O)OC(O)+ + CF3 and the dominant, sequential reaction CF3CO+ + CF3 + CO2. Calculations revealed a low-energy isomer of ionized TFAN, incorporating the three moieties CF3CO+, CF3, and CO2 joined in a noncovalent complex, mediating its unimolecular dissociation.

Gas-Phase Reaction between CF2O and CF3C(O)OH: Characterization of CF3C(O)OC(O)F.

The thermal decomposition of trifluoroacetic acid and carbonyl fluoride (CF2O) has been extensively studied because of their importance in the oxidation of hydrochlorofluorocarbons in the atmosphere. We hitherto present the study of the thermal reaction between these two molecules. The reaction mechanism was studied using Fourier transform infrared spectroscopy in the temperature range of 513-573 K. The reaction proceeds homogeneously in the gas phase through the formation of a reaction intermediate, here characterized as CF3C(O)OC(O)F (detected for the first time in this work), the major final products being CF3C(O)F, HF, and CO2. We demonstrate that the reaction is first-order with respect to each reagent, second-order global and the mechanism consists of two steps, the first being the rate-determining one. The Ea = 110.1 ± 6.1 kJ mol-1 and A = (1.2 ± 0.2) × 10-12 cm3 molec-1 s-1 values were obtained from the experimental data. The low activation energy is explained by the hydrogen-bond interactions between the -OH group of the acid and the F atom of the CF2O. First-principles calculations at the G4MP2 level of theory were carried out to understand the dynamics of the decomposition. Thermodynamic activation values found for this reaction are as follows: Δ H⧧ = 105.6 ± 6.4 kJ mol-1, Δ S⧧ = -88.6 ± 9.7 J mol-1 K-1, and Δ G⧧ = 153.7 ± 13.5 kJ mol-1. The comparison between theory and experimental results showed excellent similarities, thus strengthening the proposed mechanism.

Reaction of Methyl Fluoroformyl Peroxycarbonate (FC(O)OOC(O)OCH3) with Cl Atoms: Formation of Hydro-ChloroFluoro-Peroxides.

The products following Cl atom initiated reactions of FC(O)OOC(O)OCH3 in 50-760 Torr of N2 at 296 K were investigated using FTIR. Reaction of Cl atoms with methyl fluoroformyl peroxycarbonate proceeds mainly via attack at the methyl group, forming FC(O)OOC(O)OCH2• radicals. Further reaction of this kind of radical with Cl2 forms three new compounds: FC(O)OOC(O)OCH2Cl, FC(O)OOC(O)OCHCl2, and FC(O)OOC(O)OCCl3, whose existence was characterized experimentally by FTIR spectroscopy assisted by ab initio calculations at the B3LYP/6-31++G(d,p) level. Relative rate techniques were used to measure k(Cl+FC(O)OOC(O)OCH3) = (4.0 ± 0.4) × 10-14 cm3 molecule-1 s-1 and k(Cl+FC(O)OOC(O)OCH2Cl) = (3.2 ± 0.3) × 10-14 cm3 molecule-1 s-1. When the reaction is run in the presence of oxygen, the paths giving chlorinated peroxide formation are suppressed, and oxidation to (mainly) CO2 and HCl takes place through highly oxidized intermediates with lifetimes long enough to be detected by FTIR spectroscopy.

Properties and thermal decomposition of the hydro-fluoro-peroxide CH3OC(O)OOC(O)F.

The thermal decomposition of methyl fluoroformyl peroxycarbonate CH3OC(O)OOC(O)F was studied in the range of 30- 96 °C using FTIR spectroscopy to follow the course of the reaction in the presence of either N2, O2, or CO as bath gases. The rate constants of the homogeneous first-order process fit the Arrhenius equation k(exp) = (5.4 ± 0.2) × 10(14) exp[-(27.1 ± 0.6 kcal mol(-1)/RT)] (in units of s(-1)). A complete mechanism of decomposition is presented. An experimental O-O bond energy of 27 ± 1 kcal mol(-1) was obtained. The products observed when N2 or O2 are used as bath gases were CO2, CO, HF, and CH3OC(O)H, while in the presence of CO, CH3OC(O)F was also observed. Transition state ab initio calculations were carried out to understand the dynamics of the decomposition. Additionally, thermodynamic properties of the atmospherically relevant CH3OCO2• radical were calculated. The heat of formation, ΔH°(f 298), obtained for CH3OCO2• and CH3OC(O)OOC(O)F, were 78 ± 3 kcal mol(-1) and 191 ± 5 kcal mol(-1), respectively.

Mechanism of photo-oxidation of heptafluorobutyric anhydride in the presence of NO2. Synthesis and characterization of heptafluoropropyl peroxynitrate, CF3CF2CF2OONO2.

The photolysis of heptafluorobutyric anhydride at 254 nm in the presence of NO(2) and O(2) has been studied. It leads to the formation of CF(3)CF(2)CF(2)OONO(2), CF(3)CF(2)OONO(2), and CF(2)O as the only fluorine-containing carbonaceous products. The formation of the new heptafluoropropyl peroxynitrate (HFPN, CF(3)CF(2)CF(2)OONO(2)), as one of the main products, is a consequence of the formation of CF(3)CF(2)CF(2)OO(•) radicals followed by the reaction with NO(2). To characterize HFPN, the UV absorption cross sections and their temperature dependence between 245 and 300 K have been measured over the wavelength range 200-300 nm as well as the infrared absorption cross sections. Kinetic parameters for its thermal decomposition are also presented in the temperature range between 281 and 300 K. The Rice-Ramsperger-Kassel-Marcus calculation reveals that the rate coefficient for the thermal decomposition at 285 K is almost independent of total pressure. The mechanism for the decomposition of CF(3)CF(2)CF(2)OONO(2) in the presence of NO was adjusted by a kinetic model, which enabled the calculation of important rate coefficients.

2-Chloroethylisocyanate. Thermal decomposition and spectroscopic properties.

2-Chloroethylisocyanate has been studied in a thorough way. NMR, Raman, FTIR, and Ar-matrix vibrational spectra of the molecule are presented and discussed with the complement of ab initio and DFT methods. The spectroscopic results reveal the existence of anti and gauche conformers that are equally populated in the gas phase. Thermal decomposition between 393 and 648 K shows two different pathways depending on the temperature, which can be interpreted in terms of simple second- and first-order mechanisms, respectively. Quantum mechanical calculations reproduce the experimental results.