Photochemical processes on chloromethyl formate and vinyl formate in low-temperature matrices: infrared spectra and ab initio calculations on chloromethanol and vinyl alcohol

Kunttu, Henrik; Dahlqvist, Martti; Murto, Juhani; Räsänen, Markku

doi:10.1021/j100317a024

Cited by 32 publications

(30 citation statements)

References 7 publications

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“…Chloromethanol is known to decompose in the dark to formaldehyde (H 2 CO) and HCl products in both the gas phase 86,87 and in the condensed phase ͑e.g., low temperature matrices͒. 88 In so far as iodomethanol (CH 2 IOH) behaves such as chloromethanol (CH 2 ClOH) then one would expect iodomethanol (CH 2 IOH) to decay into H 2 CO and HI products consistent with step 4 of the proposed reaction mechanism. Recent ab initio calculations showed that iodomethanol (CH 2 IOH) undergoes a water assisted HI elimination reaction to produce H 2 CO and HI products and this provides further support for step 4 of the reaction mechanism.…”

Section: Water-catalyzed Hi Elimination Reaction Of Ch 2 I(oh) With Hmentioning

confidence: 96%

Comparison of the dehalogenation of polyhalomethanes and production of strong acids in aqueous and salt (NaCl) water environments: Ultraviolet photolysis of CH2I2

Guan

et al. 2004

The Journal of Chemical Physics

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The ultraviolet photolysis of CH(2)I(2) was studied in water and salt water solutions using photochemistry and picosecond time-resolved resonance Raman spectroscopy. Photolysis in both types of environments produces mainly CH(2)(OH)(2) and HI products. However, photolysis of CH(2)I(2) in salt water leads to the formation of different products/intermediates (CH(2)ICl and Cl(2) (-)) not observed in the absence of salt in aqueous solutions. The amount of CH(2)(OH)(2) and HI products appears to decrease after photolysis of CH(2)I(2) in salt water compared to pure water. We briefly discuss possible implications of these results for photolysis of CH(2)I(2) and other polyhalomethanes in sea water and other salt aqueous environments compared to nonsalt water solvated environments.

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Section: Water-catalyzed Hi Elimination Reaction Of Ch 2 I(oh) With Hmentioning

confidence: 96%

Comparison of the dehalogenation of polyhalomethanes and production of strong acids in aqueous and salt (NaCl) water environments: Ultraviolet photolysis of CH2I2

Guan

et al. 2004

The Journal of Chemical Physics

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“…Photolysis of an ion-irradiated H O ϩ C H 2 2 2 sample caused the 1145 cm Ϫ1 band to go through the same type of rise and fall shown in Figure 2. Kunttu et al (1988) showed that UV photolysis of vinyl formate produces CO and VA according to the following reaction:…”

Section: Alternate Synthesesmentioning

confidence: 99%

“…VA has been made in the past by pyrolysis of larger compounds, such as 2-chloroethanol (Joo, Merer, & Clouthier 1999), UV photolysis of vinyl formate (Kunttu et al 1988), and UV photolysis of in an argon matrix (Hawkins O 1983). These experiments all show that VA has an intense IR absorption around 1100 cm Ϫ1 , corresponding to its n 9 vibration.…”

Section: Spectral Assignmentmentioning

confidence: 99%

Solid-Phase Formation of Interstellar Vinyl Alcohol

Hudson

Moore

2003

The Astrophysical Journal

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Motivated by the recent discovery of gas-phase interstellar vinyl alcohol, CH 2 uCH(OH), we present laboratory experiments on this molecule's solid-phase formation. Through a combination of reaction chemistry, infrared spectroscopy, isotopic substitution, thermal annealings, and independent syntheses, we have identified vinyl alcohol in proton-irradiated ices and have measured its column density at ∼15 K. UV photolysis of H O ϩ C H 2 2 2 ices at ∼15 K also produces vinyl alcohol. It is suggested that vinyl alcohol is formed in interstellar H O ϩ C H 2 2 2 ices and then ejected into the gas phase, where it might undergo additional reactions.

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“…Similar equilibration of conformers due to UV irradiation has been found for various formic acid esters. 38 At the present time no explanation is available for this difference in photochemical equilibrium at different wavelengthsmthe mechanism for interconversion after electronic excitation may differ much from that after vibrational excitation. Figure 4 displays the potential energy surface for 2-NE, calculated at the 3-21G basis set level.…”

Section: C3mentioning

confidence: 93%

Infrared Induced Conformer Interconversion Processes in Low‐Temperature Matrices

1988

Self Cite

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Molecules embedded in low-temperature matrices experience conformer interconversion processes due to IR- (or UV-)irradiation. This paper summarizes the known IR-induced conformational changes, of which the majority has been studied by using broad-band sources provided with filters. We focus at the thermal and IR-photochemical methods in obtaining information of conformational energetics of matrix isolated molecules, at the usefulness of ab initio calculations in assigning the spectra of conformers involved and in finding the reaction path on the ground state surface. The data obtained from a number of molecules is used to discuss possible mechanisms in both intramolecularly hydrogen-bonded and non-bonded molecules. Also possible indications of mode-selective phenomena in these processes are dealt with. In addition, common trends found for photorotamerization in different hosts are discussed.

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Photochemical processes on chloromethyl formate and vinyl formate in low-temperature matrices: infrared spectra and ab initio calculations on chloromethanol and vinyl alcohol

Cited by 32 publications

References 7 publications

Comparison of the dehalogenation of polyhalomethanes and production of strong acids in aqueous and salt (NaCl) water environments: Ultraviolet photolysis of CH2I2

Comparison of the dehalogenation of polyhalomethanes and production of strong acids in aqueous and salt (NaCl) water environments: Ultraviolet photolysis of CH2I2

Solid-Phase Formation of Interstellar Vinyl Alcohol

Infrared Induced Conformer Interconversion Processes in Low‐Temperature Matrices

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