Photoacid Generators Activated Through Sequential Two-Photon Excitation: 1-Sulfonatoxy-2-alkoxyanthraquinone Derivatives

Two sulfonate ester derivatives of anthraquinone, 1-tosyloxy-2-methoxy-9,10-anthraquinone (<b>1a</b>) and 1-trifluoromethylsulfonoxy-2-methoxy-9,10-anthraquinone (<b>1b</b>) were prepared and their ability to produce strong acids upon photoexcitation was examined. It is shown that these compounds generate acid with a yield that increases with light intensity when the applied photon dose is held constant. Additional experiments show that the rate of acid generation increases 4 fold when visible light (532 nm) laser pulses are combined with ultraviolet (355 nm) compared with ultraviolet alone. Continuous wave diode laser photolysis also effects acid generation with a rate that depends quadratically on the light intensity. Density functional theory calculations, laser flash photolysis, and chemical trapping experiments support a mechanism whereby an initially formed triplet state (T₁) is excited to a higher triplet state which in turn undergoes homolysis of the RS(O₂)–OAr bond. Secondary reactions of the initially formed sulfonyl radicals produce strong acids. It is demonstrated that high intensity photolysis of either <b>1a </b>or <b>1b</b> can initiate cationic polymerization of ethyl vinyl ether.

Photoacid Generators Activated Through Sequential Two-Photon Excitation: 1-Sulfonatoxy-2-alkoxyanthraquinone Derivatives

Two sulfonate ester derivatives of anthraquinone, 1-tosyloxy-2-methoxy-9,10-anthraquinone (<b>1a</b>) and 1-trifluoromethylsulfonoxy-2-methoxy-9,10-anthraquinone (<b>1b</b>) were prepared and their ability to produce strong acids upon photoexcitation was examined. It is shown that these compounds generate acid with a yield that increases with light intensity when the applied photon dose is held constant. Additional experiments show that the rate of acid generation increases 4 fold when visible light (532 nm) laser pulses are combined with ultraviolet (355 nm) compared with ultraviolet alone. Continuous wave diode laser photolysis also effects acid generation with a rate that depends quadratically on the light intensity. Density functional theory calculations, laser flash photolysis, and chemical trapping experiments support a mechanism whereby an initially formed triplet state (T₁) is excited to a higher triplet state which in turn undergoes homolysis of the RS(O₂)–OAr bond. Secondary reactions of the initially formed sulfonyl radicals produce strong acids. It is demonstrated that high intensity photolysis of either <b>1a </b>or <b>1b</b> can initiate cationic polymerization of ethyl vinyl ether.

Computational Study on the Mechanism of Cycloaddition Reactions of Bissulfonyl-1,3-butadiene with Some Alkenes

The cycloaddition reactions of 2,3-bis (ethylene sulfonyl)-1,3-butadiene with 2,3-dimethyl- 1,3-butadiene, cyclopentadiene, 2-methyl prop-2-enoate and ethyl vinyl ether have been theoretically studied using the DFT method at the MPWB1K/cc-pVDZ level of theory. There are two possible modes of participation in each reaction (2π and 4π electron), of which the 2π electron is preferred. The energy results indicate that formations of the [2+4] cycloadducts are favored kinetically. The stereoselectivity of the [2+4] cycloaddition reaction of 2,3-bis (ethylene sulfonyl)-1,3-butadiene with cyclopentane is the highest and the energy barrier for this process is the lowest.

Successive Activation of C–H and C–O Bonds of Vinyl Ethers by a Diphosphine and Hydrido-Bridged Diiridium Complex

The reaction of [(Cp*Ir)2(μ-dmpm)(μ-H)][OTf] (2) [Cp* = η5-C5Me5, dmpm = bis(dimethylphosphino)methane] with 2,3-dihydrofuran gives [(Cp*IrH)2(μ-dmpm){μ-(2,3-dihydrofuranyl)}][OTf] (3) in an isolated yield of 70% via the C–H bond activation at the 5-position of 2,3-dihydrofuran. Complex 3 is slowly converted into [(Cp*Ir)2(μ-dmpm)(μ-C=C(H)CH2CH2OH)][OTf] (4) quantitatively via the proton-mediated C–O bond activation. The reaction of 2 with ethyl vinyl ether gives [(Cp*Ir)2(μ-dmpm)(μ-CH=CH2)][OTf] (5) in the isolated yield of 64% via the successive activation of C–H and C–O bonds.

Isomer Identification in Flames with Double-Imaging Photoelectron/Photoion Coincidence Spectroscopy (i2PEPICO) using Measured and Calculated Reference Photoelectron Spectra

Double-imaging photoelectron/photoion coincidence (i2PEPICO) spectroscopy using a multiplexing, time-efficient, fixed-photon-energy approach offers important opportunities of gas-phase analysis. Building on successful applications in combustion systems that have demonstrated the discriminative power of this technique, we attempt here to push the limits of its application further to more chemically complex combustion examples. The present investigation is devoted to identifying and potentially quantifying compounds featuring five heavy atoms in laminar, premixed low-pressure flames of hydrocarbon and oxygenated fuels and their mixtures. In these combustion examples from flames of cyclopentene,iso-pentane,iso-pentane blended with dimethyl ether (DME), and diethyl ether (DEE), we focus on the unambiguous assignment and quantitative detection of species with the sum formulae C5H6, C5H7, C5H8, C5H10, and C4H8O in the respective isomer mixtures, attempting to provide answers to specific chemical questions for each of these examples. To analyze the obtained i2PEPICO results from these combustion situations, photoelectron spectra (PES) from pure reference compounds, including several examples previously unavailable in the literature, were recorded with the same experimental setup as used in the flame measurements. In addition, PES of two species where reference spectra have not been obtained, namely 2-methyl-1-butene (C5H10) and the 2-cyclopentenyl radical (C5H7), were calculated on the basis of high-levelab initiocalculations and Franck-Condon (FC) simulations. These reference measurements and quantum chemical calculations support the early fuel decomposition scheme in the cyclopentene flame towards 2-cyclopentenyl as the dominant fuel radical as well as the prevalence of branched intermediates in the early fuel destruction reactions in theiso-pentane flame, with only minor influences from DME addition. Furthermore, the presence of ethyl vinyl ether (EVE) in DEE flames that was predicted by a recent DEE combustion mechanism could be confirmed unambiguously. While combustion measurements using i2PEPICO can be readily obtained in isomer-rich situations, we wish to highlight the crucial need for high-quality reference information to assign and evaluate the obtained spectra.

Products and mechanism of the OH-initiated photo-oxidation of perfluoro ethyl vinyl ether, C2F5OCFCF2

The photo-oxidation of PEVE in 1 bar of air in the presence of NOx results in the formation of C2F5OCFO, FC(O)C(O)F and CF2O in molar yields of 0.50, 0.46 and 1.50, respectively.