Radiation chemistry of the carbon–halogen bond

Bühler, Rolf E.

doi:10.1002/9780470771280.ch12

Cited by 16 publications

(8 citation statements)

References 185 publications

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“…Indeed, the DEA process is thought to be responsible for carbon-halogen bond cleavage in the radiolysis of organohalides [118]. Our experimental data also indicate that DEA activated by low-energy secondary electrons is the major mechanism of halocarbon decomposition in ice films [14,27], based on the observation that bond-breaking in condensed CF 2 Cl 2 is selective towards C-Cl bond cleavage.…”

Section: Electron-stimulated Decomposition Of the Halocarbon Parentsupporting

confidence: 62%

Electron-driven chemistry of halogenated compounds in condensed phases: Effects of solvent matrices on reaction dynamics and kinetics

Perry¹,

Faradzhev²,

Fairbrother³

et al. 2004

International Reviews in Physical Chemistry

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Section: Electron-stimulated Decomposition Of the Halocarbon Parentsupporting

confidence: 62%

Electron-driven chemistry of halogenated compounds in condensed phases: Effects of solvent matrices on reaction dynamics and kinetics

Perry¹,

Faradzhev²,

Fairbrother³

et al. 2004

International Reviews in Physical Chemistry

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“…Such probe molecules are rare, thus in this work we took a different approach. Halogenated molecules will form stable radical cations but are well-known to detach a halide anion on electron attachment, − typically leaving a nonabsorbing radical. The key was to choose molecules for which dissociation is rapid, to avoid interfering absorption of the radical anion prior to dissociation.…”

Section: Resultsmentioning

confidence: 99%

Sub-picosecond Production of Solute Radical Cations in Tetrahydrofuran after Radiolysis

Cook

2021

J. Phys. Chem. A

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Ultrafast hole transfer from solvent radical cations produced by radiolysis with ∼10 ps, 9 MeV electron pulses to solutes in tetrahydrofuran (THF) was investigated. Because of rapid fragmentation of initially produced THF +• , solute radical cations are not expected and have not previously been reported. When 9,9-dihexyl-2,7-dibromofluorene (Br 2 F) at 5 to 1000 mM was used, Br 2 F +• with radiation chemical yields up to G = 2.23/100 eV absorbed was observed. While more than half of this was the result of direct solute ionization, the results highlight the importance of capturing holes from THF +• prior to solvation and fragmentation. The observed data show a time-resolution limited (15 ps) rise in transient absorption of Br 2 F +• , identical in form to reports of presolvated or dry electron capture in water and a few organic liquids, including THF. The results were thus interpreted with a similar formalism, finding C 37 = 1.7 M, the concentration at which 37% of holes escape capture. The yield of solvent hole capture can be accounted for by the formation of solvent holes adjacent to solute molecules reacting faster than they can fragment; however, mechanisms such as delocalized holes or rapid hopping may play a role. Low temperature results find over two times more capture, supporting the speculation that if THF +• was longer lived, the yield of capture in under 15 ps would have been at least 2 times larger at 1 M Br 2 F, possibly capturing nearly all available holes from the solvent.

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“…However, there are aspects of this method that make it difficult to obtain products in high yield. Upon reduction, CHCl 3 fragments to Cl - and • CHCl 2 . Evidence for side reactions involving the • CHCl 2 radical can be found in the formation of CH 3 Cl by Arbuzov reaction of P(OMe) 3 ligands .…”

Section: Resultsmentioning

confidence: 99%

Oxidation of Metal Carbynes in the Presence of Alkynes. Alkyne Addition vs H-Shift in the Carbene Intermediate

1998

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One-electron oxidation of the carbyne complex (η 5 -C 5 H 5 )(CO){P(OPh) 3 }MotCCH 2 CH 2 CH 2 -CH 3 (1a) in the presence of phenylacetylene results in H-abstraction and addition of the alkyne to the resulting metal carbene. The final product of the addition is the η 1 η 2 -allyl complex (η 5 -C 5 H 5 )(CO){P(OPh) 3 }Mo[η 1 :η 2 -CH{P(OPh) 3 }C(Ph)dCH(CH 2 CH 2 CH 2 CH 3 )] (2a), the structure of which was confirmed by X-ray crystallography.Supporting Information Available: Tables of bond distances, bond angles, positional parameters, and anisotropic displacement parameters for 2a (16 pages). See any current masthead page for ordering information and Web access instructions.OM980534X

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Radiation chemistry of the carbon–halogen bond

Cited by 16 publications

References 185 publications

Electron-driven chemistry of halogenated compounds in condensed phases: Effects of solvent matrices on reaction dynamics and kinetics

Electron-driven chemistry of halogenated compounds in condensed phases: Effects of solvent matrices on reaction dynamics and kinetics

Sub-picosecond Production of Solute Radical Cations in Tetrahydrofuran after Radiolysis

Oxidation of Metal Carbynes in the Presence of Alkynes. Alkyne Addition vs H-Shift in the Carbene Intermediate

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