ChemInform Abstract: PHOTOOXIDATION OF CHLOROFORM: ISOLATION AND CHARACTERIZATION OF TRICHLOROMETHYL HYDROPEROXIDE

Gaeb, S.; Turner, Wayne

doi:10.1002/chin.198519156

Cited by 2 publications

(2 citation statements)

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“…[22][23][24] This is a good one-electron oxidizing agent, 25-32 as is the subsequently formed trichloromethylhydroperoxide. 29, 33 The latter can react with an oxidizable substrate (S), which may be a metal ion such as Fe 2+ or an organic species, breaking the O-O bond. 34 The unstable trichloromethanol formed through hydrogen abstraction by the trichloromethoxy radical yields phosgene which, in the presence of water, slowly hydrolyzes.…”

Section: Resultsmentioning

confidence: 99%

Photocatalysis by tetraphenylporphyrin of the decomposition of chloroform

Muñoz

Cohen

Linh-Trung

et al. 2008

Photochem Photobiol Sci

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Irradiation of solutions of tetraphenylporphyrin (H2TPP) in chloroform causes decomposition of the chloroform at UV wavelengths higher than those that decompose chloroform directly. The catalytic cycle involves photooxidation of the porphyrin followed by thermal reduction. Photocatalysis continues after H2TPP has been completely protonated by the HCl produced during decomposition, and the rate of HCl production accelerates as a second pathway, in which CCl3OOH oxidizes the porphyrin, becomes important.

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Section: Resultsmentioning

confidence: 99%

Photocatalysis by tetraphenylporphyrin of the decomposition of chloroform

Muñoz

Cohen

Linh-Trung

et al. 2008

Photochem Photobiol Sci

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“…More HCl is formed during the subsequent decomposition of trichloromethylhydroperoxide, formed from the addition of O 2 to CCl 3 , followed by another hydrogen abstraction from chloroform (14–17). The absorbance of CHCl 3 was found to be 0.080 (measured against ethanol) for a 1 cm path length at 254 nm.…”

Section: Resultsmentioning

confidence: 99%

The Photolysis of Chlorocarbonylbis(triphenylphosphine)iridium(I) in Chloroform

Witter

Karabulut

Hoggard³

2008

Photochem & Photobiology

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Under 254 or 313 nm irradiation in chloroform, [IrCl(CO)(PPh3)2] is converted cleanly to [IrCl2(CO)H(PPh3)2] through the addition of HCl, produced photochemically. Under 254 nm irradiation, some of the reaction of [IrCl(CO)(PPh3)2] occurs by direct photolysis of chloroform, though a greater contribution arises from a reaction initiated through absorption of light by the metal complex. Under 313 nm irradiation, essentially all of the reaction is metal-initiated. The linear dependence of the reaction rate on light intensity and on the fraction of light absorbed by the Ir(I) complex as well as the lack of a deuterium isotope effect rule out a radical process. Instead it is proposed that an association complex between excited state [IrCl(CO)(PPh3)2] and CHCl3 leads to dissociation of a chlorine atom from CHCl3, yielding HCl after abstraction of a hydrogen from another CHCl3. HCl then adds to a ground state [IrCl(CO)(PPh3)2] complex.

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ChemInform Abstract: PHOTOOXIDATION OF CHLOROFORM: ISOLATION AND CHARACTERIZATION OF TRICHLOROMETHYL HYDROPEROXIDE

Cited by 2 publications

References 1 publication

Photocatalysis by tetraphenylporphyrin of the decomposition of chloroform

Photocatalysis by tetraphenylporphyrin of the decomposition of chloroform

The Photolysis of Chlorocarbonylbis(triphenylphosphine)iridium(I) in Chloroform

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