Abstract
The FeCl4− ion, heterogenized on a Dowex ion exchange resin, catalyzes the aerobic photodecomposition of neat CH2Cl2. Phosgene production was used to characterize the extent of decomposition, although it appears to be a secondary product from the decomposition of chloroform, which is suggested to arise from the reaction of dichloromethanol with hydrogen chloride. The yield of CHCl3 increases when the production of phosgene is suppressed by water or acetonitrile. CuCl42−, likewise heterogenized on Dowex, is photocatalytically inactive.
Similar content being viewed by others
Notes and references
D. Diaz Diaz, P. O. Miranda, J. I. Padron and V. S., Martin, Recent uses of iron(iii) chloride in organic synthesis Curr. Org. Chem. 2006 10 457–476
P. E. Hoggard, M. Gruber and A., Vogler, The photolysis of iron(iii) chloride in chloroform Inorg. Chim. Acta 2003 346 137–142
O. Horvath and A., Vogler, Photoredox chemistry of chloromercurate(ii) complexes in acetonitrile Inorg. Chem. 1993 32 5485–5489
K. Oldenburg and A., Vogler, Electronic spectra and photochemistry of tin(ii), lead(ii), antimony(iii), and bismuth(iii) bromide complexes in solution Z. Naturforsch., B: Chem. Sci. 1993 48 1519–1523
K. Oldenburg and A., Vogler, Photoredox chemistry of bismuth trichloride in benzene J. Organomet. Chem. 1996 515 245–248
A. Vogler and A., Paukner, Photoredox chemistry of chloro complexes of antimony(iii) and (v) Inorg. Chim. Acta 1989 163 207–211
L. Sheps, A. C. Crowther, C. G. Elles and F. F., Crim, Recombination dynamics and hydrogen abstraction reactions of chlorine radicals in solution J. Phys. Chem. A 2005 109 4296–4302
K. Takaki, J. Yamamoto, K. Komeyama, T. Kawabata and K., Takehira, Photocatalytic oxidation of alkanes with dioxygen by visible light and copper(ii) and iron(iii) chlorides: preference oxidation of alkanes over alcohols and ketones Bull. Chem. Soc. Jpn. 2004 77 2251–2255
K. Takaki, J. Yamamoto, Y. Matsushita, H. Morii, T. Shishido and K., Takehira, Oxidation of alkanes with dioxygen induced by visible light and Cu(ii) and Fe(iii) chlorides Bull. Chem. Soc. Jpn. 2003 76 393–398
G. B. Shul’pin, G. V. Nizova and Y. N., Kozlov, Photochemical aerobic oxidation of alkanes promoted by iron complexes New J. Chem. 1996 20 1243–1256
L. Wang, J. Li, Y. Lv, G. Zhao and S., Gao, Selective aerobic oxidation of alcohols catalyzed by iron chloride hexahydrate/TEMPO in the presence of silica gel Appl. Organomet. Chem. 2011 26 37–43
M., Barbier, Selective photoinduced oxidation of benzylic methylene groups through UV irradiation in presence of ferric chloride Helv. Chim. Acta 1984 67 866–869
D., Brox, Selektive Chlorierung von Benzol zu Monochlorbenzol in der Gasphase Monatsberichte Deutschen Akad. Wissenschaften Berlin 1961 3 643–649
A. Maldotti, G. Varani and A., Molinari, Photo-assisted chlorination of cycloalkanes with iron chloride heterogenized with Amberlite Photochem. Photobiol. Sci. 2006 5 993–995
A. M. Chan, L. A. Peña, L. R. Cohen, K. Hou, B. M. Harvey and P. E., Hoggard, Catalysis of the photodecomposition of chloroform by a polystyrene anion exchange resin Curr. Catal. 2013 2 79–87
K. J. Doyle, H. Tran, M. Baldoni-Olivencia, M. Karabulut and P. E., Hoggard, Photocatalytic degradation of dichloromethane by chlorocuprate(ii) ions Inorg. Chem. 2008 47 7029–7034
V. Catoire, R. Lesclaux, W. F. Schneider and T. J., Wallington, Kinetics and mechanisms of the self-reactions of CCl3O2 and CHCl2O2 radicals and their reactions with HO2J. Phys. Chem. 1996 100 14356–14371
R. Lesclaux, A. M. Dognon and F., Caralp, Photooxidation of halomethanes at low temperature: the decomposition rate of CCl3O and CFCl2O radicals J. Photochem. Photobiol., A 1987 41 1–11
S. Gäb and W. V., Turner, Photooxidation of chloroform: isolation and characterization of trichloromethyl hydroperoxide Angew. Chem. 1985 97 48
W. V. Turner and S., Gaeb, Preparation of 1-chloroalkyl hydroperoxides by the addition of hydrogen chloride to carbonyl oxides J. Org. Chem. 1992 57 1610–1613
V. D. Knyazev and I. R., Slagle, Thermochemistry of the R-O2 bond in alkyl and chloroalkyl peroxy radicals J. Phys. Chem. A 1998 102 1770–1778
H. Sun, C.-J. Chen and J. W., Bozzelli, Structures, intramolecular rotation barriers, and thermodynamic properties (enthalpies, entropies and heat capacities) of chlorinated methyl hydroperoxides (CH2ClOOH, CHCl2OOH, and CCl3OOH) J. Phys. Chem. A 2000 104 8270–8282
U.S. Environmental Protection Agency, Basic information about dichloromethane in drinking water, http://water.epa.gov/drink/contaminants/basicinformation/dichloromethane.cfm, accessed 28 May 2013
Environmental Working Group, National Drinking Water Database, http://www.ewg.org/tap-water/, accessed 28 May 2013
B. Chen, W. Lee, P. K. Westerhoff, S. Krasner and P., Herckes, Solar photolysis kinetics of disinfection byproducts Water Res. 2010 44 3401–3409
H. Du, R.-C. A. Fuh, J. Li, L. A. Corkan and J. S., Lindsey, Photochem CAD: a computer-aided design and research tool in photochemistry Photochem. Photobiol. 1998 68 141–142
J. S. Lindsey, PhotochemCAD, spectra recorded by Junzhong Li and Richard W. Wagner, http://omlc.ogi.edu/spectra/PhotochemCAD/html/index.html, accessed April 1, 2013
A. Stone and E. B., Fleischer, The molecular and crystal structure of porphyrin diacids J. Am. Chem. Soc. 1968 90 2735–2748
B. M. Harvey and P. E., Hoggard, Determination of micromolar concentrations of strong acids in chloroform by protonation of tetraphenylporphyrin Monatsh. Chem. 2012 143 1101–1105
J. C. Olsen, G. E. Ferguson, V. J. Sabetta and L., Scheflan, Quantitative determination of phosgene Ind. Eng. Chem. 1931 3 189–191
T. H. Nguyen, P. J. Shannon and P. E., Hoggard, Kinetics of the photooxidation of tris(bipyridine)iron(ii) in chloroform Inorg. Chim. Acta 1999 291 136–141
P. Day and C. K., Jorgensen, A simple molecular orbital model of transition-metal halide complexes J. Chem. Soc. 1964 6226–6234
J. Borisch, S. Pilkenton, M. L. Miller, D. Raftery and J. S., Francisco, TiO2 Photocatalytic degradation of dichloromethane: An FTIR and solid-state NMR study J. Phys. Chem. B 2004 108 5640–5646
N. N. Lichtin and M., Avudaithai, TiO2-photocatalyzed oxidative degradation of CH3CN, CH3OH, C2HCl3, and CH2Cl2 supplied as vapors and in aqueous solution under similar conditions Environ. Sci. Technol. 1996 30 2014–2020
M. L. Miller, J. Borisch, D. Raftery and J. S., Francisco, Changing the product state distribution and kinetics in photocatalytic surface reactions using pulsed laser irradiation J. Am. Chem. Soc. 1998 120
R. M. Alberici, M. A. Mendes, W. F. Jardim and M. N., Eberlin, Mass spectrometry on-line monitoring and MS2 product characterization of TiO2/UV photocatalytic degradation of chlorinated volatile organic compounds J. Am. Soc. Mass Spectrom. 1998 9 1321–1327
P. Calza, C. Minero and E., Pelizzetti, Photocatalytic transformations of chlorinated methanes in the presence of electron and hole scavengers J. Chem. Soc., Faraday Trans. 1997 93 3765–3771
T. Hisanaga, K. Harada and K., Tanaka, Photocatalytic degradation of organochlorine compounds in suspended titanium dioxide J. Photochem. Photobiol., A 1990 54 113–118
J. F. Tanguay, R. W. Coughlin and S. L., Suib, Photodegradation of dichloromethane with titanium catalysts ACS Symp. Ser. 1990 437 114–118
J. F. Tanguay, S. L. Suib and R. W., Coughlin, Dichloromethane photodegradation using titanium catalysts J. Catal. 1989 117 335–347
S. Rodrigues, Photocatalytic remediation, in Nanoscale Materials in Chemistry, ed. K. J. Klabunde and R. M. Richards, Wiley, Hoboken, NJ, 2nd edn, 2009, pp. 629-646
K. Brudnik, J. T. Jodkowski, D. Sarzynski and A., Nowek, Mechanism of the gas-phase decomposition of trifluoro-, trichloro-, and tribromomethanols in the presence of hydrogen halides J. Mol. Model. 2011 17 2395–2409
H. Sun and J. W., Bozzelli, Structures, intramolecular rotation barriers, and thermochemical properties of radicals derived from H Atom Loss in Mono-, Di-, and trichloromethanol and parent chloromethanols J. Phys. Chem. A 2001 105 4504–4516
P. E. Hoggard and A., Maldotti, Catalysis of the photodecomposition of carbon tetrachloride in ethanol by an amberlite anion exchange resin J. Catal. 2010 275 243–249
E. M. Glebov, V. F. Plyusnin, V. P. Grivin, Y. V. Ivanov, N. V. Tkachenko and H., Lemmetyinen, Mechanism of Br2− and Cl2− radical anions formation upon IrCl62− photoreduction in methanol solutions containing free Br− and Cl− ions J. Photochem. Photobiol., A 1998 113 103–112
R. Michalski, A. Sikora, J. Adamus and A., Marcinek, Dihalide and pseudohalide radical anions as oxidizing agents in nonaqueous solvents J. Phys. Chem. A 2010 114 861–866
V. Nagarajan and R. W., Fessenden, Flash-photolysis of transient radicals. 1. Cl2−, Br2−, I2−, and SCN2−J. Phys. Chem. 1985 89 2330–2335
X. Y., Yu, Critical evaluation of rate constants and equilibrium constants of hydrogen peroxide photolysis in acidic aqueous solutions containing chloride ions J. Phys. Chem. Ref. Data 2004 33 747–763
H. G. Libuda, F. Zabel, E. H. Fink and K. H., Becker, Formyl chloride: UV absorption cross sections and rate constants for the reactions with Cl and OH J. Phys. Chem. 1990 94 5860–5865
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Chan, A.M., Harvey, B.M. & Hoggard, P.E. Photodecomposition of dichloromethane catalyzed by tetrachloroferrate(iii) supported on a Dowex anion exchange resin. Photochem Photobiol Sci 12, 1680–1687 (2013). https://doi.org/10.1039/c3pp50094b
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1039/c3pp50094b