Charge Transfer from the Carbon Tetrachloride Radical Cation to Alkyl Chlorides, Alkanes, Alkenes and Aromatics

Mehnert, R.; Brede, O.; Bös, J.; Naumann, W.

doi:10.1002/bbpc.19790831008

Cited by 43 publications

(14 citation statements)

References 11 publications

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“…This dissociation process should be well distinguished from the delayed transformation of the metastable ArOH + driven by a nucleophile such as Cl À formulated in eqn (8). The latter one happens on the late nanosecond scale.…”

Section: Energetics Of the Cation Dissociationmentioning

confidence: 96%

“…In general, FET represents the bimolecular electron transfer from aromatic donor molecules to parent radical cations derived from non-polar solvents such as n-alkanes, 2,3 cycloalkanes [4][5][6] and alkyl chlorides. [7][8][9] These radical cations are usually generated by photolysis (1a) as well as radiolysis (1b).…”

Section: Introductionmentioning

confidence: 99%

“…reaction (3). Alkyl chlorides were preferred as solvents because in addition to their ionization (1) they are also very efficient scavengers for the solvated electrons, 8,9 see reaction (3a).…”

Section: Introductionmentioning

confidence: 99%

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Free electron transfer—relations between molecule dynamics and reaction kinetics

Brede¹,

Naumov²

2010

Chem. Soc. Rev.

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Electron transfer in non-polar media (alkanes, alkyl chlorides) exhibits some essential peculiarities. For instance the reaction of hetero-substituted aromatics with parent solvent radical cations results in the parallel formation of metastable donor radical cations and fragmentation products, in comparable amounts. The fragmentation products originate from a dissociative donor radical cation which decays extremely rapidly, i.e., in a few femtoseconds. This phenomenon is explained in terms of intramolecular dynamic motions which cause changes of the electron density (pi- and n-orbitals) in dependence on the deformation angle between the substituents and the aromatic ring. Hence femtosecond dynamics is reflected in the nanosecond time range and can be observed with real-time spectroscopy. Therefore, the process is named free electron transfer (FET) which corresponds to an unhindered electron jump occurring in the first approach of the reactants. This dynamic controlled process is compared with the classical electron transfer theories which are based on equilibrium kinetics. From the FET mechanism some new aspects for chemical reaction kinetics can be derived (critical review, 69 references).

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Section: Energetics Of the Cation Dissociationmentioning

confidence: 96%

Section: Introductionmentioning

confidence: 99%

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Free electron transfer—relations between molecule dynamics and reaction kinetics

Brede¹,

Naumov²

2010

Chem. Soc. Rev.

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“…The parent radical cations produced in the radiolysis of alkyl chlorides (here n -BuCl, reaction 1a) and alkanes are powerful oxidants that are able to generate a vast number of secondary radical cations . They ionize molecules having lower ionization potentials than theirs (IP ≈ 9.5−10.5 eV), and hence they appear to be universal tools for the generation of solute radical cations. − Usually, this kind of one-electron oxidation is a diffusion-controlled reaction that is called free electron transfer (FET) (eq 1b) …”

Section: Introductionmentioning

confidence: 99%

Ionization of Aromatic Sulfides in Nonpolar Media: Free vs Reaction-Controlled Electron Transfer

2006

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The primary products of the bimolecular free electron transfer (FET) from aromatic sulfides (PhSCH2Ph, PhSCHPh2, PhSCPh3) to n-butyl chloride radical cations are two radical cation conformers: a dissociative and a metastable one. In analogy with formerly studied donor systems, this result seems to reflect femtosecond oscillations in the ground state of the sulfides such as torsion motions around the Ar-S bond. This motion is accompanied by a marked electron fluctuation within the HOMO (or the n) orbitals. The FET products observed in the nanosecond time scale such as the metastable sulfide radical cations (Ar-S-CR3*+), the dissociation products R3C+; and R3C*, and their (experimentally) nondetectable counterparts Ar-S* as well as Ar-S+ can be understood with the simplified assumption of two extreme conformations, namely a planar and a twisted donor molecule. Using mediator radical cations (benzene, butylbenzene, biphenyl), the stepwise reduction of the free energy of the electron transfer from -DeltaH = 2.5 to

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“…Radiation-induced electron transfer in solutions offers a convenient way for producing radical cations (S .+ ) of a high variety of solute (donor or scavenger) molecules. − As well studied for n -alkanes, cycloalkanes, and alkyl chlorides, such as butyl chlorides, dichloroethane, and carbon tetrachloride, in nonpolar solvents RX, the formed metastable parent ions react as a rule diffusion-controlled with solutes of lower ionization potential [reactions 1 and 2] It was recently found that using phenols (ArOH) or hetero analogous thiophenols and selenophenols as solutes, additionally to the expected radical cations (ArOH⎤ .+ ) in a comparable amount also heteroatom centered radicals (phenoxyls, ArO . )…”

Section: Introductionmentioning

confidence: 99%

Monitoring of the Heterogroup Twisting Dynamics in Phenol Type Molecules via Different Characteristic Free-Electron-Transfer Products

Brede¹,

Hermann²,

Naumann³

et al. 2002

J. Phys. Chem. A

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Phenol radical cations as well as phenoxyl radicals were observed as direct products of free electron transfer from phenol type solute molecules to solvent parent radical cations generated by ionizing irradiation. It is shown that the finding of the two species in comparable amounts can be explained by a nuclear-structure dependent solute cation dissociation behavior: Quantum-chemical calculations indicate that for phenol as solute primarily its conformers with perpendicular C-OH axis orientation to the aromatic ring tend to prompt deprotonation after ionization. A quite similar behavior could be predicted also for the heteroanalogous thiophenols and selenophenols. Quite generally considerable changes in the electron distribution of the groundstate molecules with the twisting angle of the -OH, -SH and -SeH groups could be calculated, with the greatest differences between "parallel" and "perpendicular" conformations. On the assumption that the fast electron-transfer projects the equilibrium solute conformer distribution onto the solute cation conformer one it is demonstrated that the experimental findings are compatible with a simple solute-cation internal relaxation model. By applying the quantum-chemically calculated conformer interconversion barrier heights it can be understood that radical fraction among the direct products increases if phenols are substituted by thiophenols or those by selenophenols, as observed in experiment.

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Charge Transfer from the Carbon Tetrachloride Radical Cation to Alkyl Chlorides, Alkanes, Alkenes and Aromatics

Cited by 43 publications

References 11 publications

Free electron transfer—relations between molecule dynamics and reaction kinetics

Free electron transfer—relations between molecule dynamics and reaction kinetics

Ionization of Aromatic Sulfides in Nonpolar Media: Free vs Reaction-Controlled Electron Transfer

Monitoring of the Heterogroup Twisting Dynamics in Phenol Type Molecules via Different Characteristic Free-Electron-Transfer Products

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