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Atomic Oxygen Anion-Radical

The ESR spectrum of the furan radical anion indicates that the Cem-0 bond is ruptured in the electron transfer process whereby the oxygen atom acquires the negative charge and the C-2 end of the open ring possesses a free radical character ... [Pg.58]

Although this mechanism could explain the inertness of di-t-butyl sulphide towards oxidation due to the absence of a-hydrogen atoms, it was later ruled out by Tezuka and coworkers They found that diphenyl sulphoxide was also formed when diphenyl sulphide was photolyzed in the presence of oxygen in methylene chloride or in benzene as a solvent. This implies that a-hydrogen is not necessary for the formation of the sulphoxide. It was proposed that a possible reactive intermediate arising from the excited complex 64 would be either a singlet oxygen, a pair of superoxide anion radical and the cation radical of sulphide 68 or zwitterionic and/or biradical species such as 69 or 70 (equation 35). [Pg.252]

The results of a recent investigation of the dependence of the cleavage rate constant upon the solvent of two similar anion radicals, those of 3-nitrobenzyl chloride and 3-chloroacetophenone,85 may likewise be interpreted as the outcome of a competition between the Lewis acid solvation of the developing halide ion and of the negatively charged oxygen atoms in the initial state. [Pg.150]

The luminol dianion Lum2< > does not exist in appreciable quantities in aqueous solvents hydrogen peroxide and a catalyst such as hemin are required. Thus another mechanism seems to be at work here. Perhaps a hydrogen atom is abstracted from the luminol monoanion Lum( > to yield a luminol radical anion 55 which then reacts with oxygen or a radical ion derived from hydrogen peroxide according to 3,4,109)... [Pg.102]

The asymmetric unit contains one [Cun(hfac)2(TTF—CH=CH—py)2]+ radical cation and one PFfi anion both in special positions, as well as one dichloromethane solvent molecule in the general position. The Cu11 ion lies in a distorted octahedral coordination, two oxygen from two hfac ions and two nitrogen from TTF CH=CH py are trans to each other and form the square plane (Cu-N bond length of 2.016(5) A) the two reminiscent oxygen atoms from the two hfac ions occupy the apical positions. [Pg.65]

It is important to emphasize that the atomic oxygen anion-radical plays a role in catalytic oxidation occnrring on varions oxide surfaces. For instance, O reacts with methane at room temperatnre over varions metal oxides (Lee and Gralowsky 1992). On solid catalysis, Q- is more reactive toward alkanes and alkenes than other ionic oxygen species. Iwamoto and Lnnsford (1980) assumed that O is the active oxygen species oxidizing benzene to phenol on with 70% selectivity at... [Pg.58]

Another common solvent that contains the oxygen atom easily available for coordination with metal cations is THE. The ability of anion-radicals to remove a proton from the position 2 of THE is sometimes a problem. Dimethyl ether is more stable as a solvent its oxygen atom is also exposed and can coordinate with a metal cation with no steric hindrance from the framing alkyl groups. An added advantage of dimethyl ether is that, because of its low boiling point (-22°C), it can be readily removed after reductive metallation and replaced by the desired solvent. The use of aromatic anion-radicals in dimethyl ether (instead of THE) is well documented (Cohen et al. 2001, references therein). [Pg.86]

Also to be mentioned are the reactions of oxygen atom radical anions with organic substrates. These reactions were reviewed by Gronert (2001). For the reactivity of the atomic oxygen anion-radical, see Section 1.7.2. The atomic oxygen anion-radical reacts with benzene, tetramethylene ethane, or cyclopentadienylidene trimethylenemethane. The reactions consist in abstraction of H2 with the formation of H2O and the corresponding distonic anion-radicals as products. [Pg.165]

To prevent the dimerization and by-product formations, Rautenstrauch et al. (1981) proposed to protonate the ketone anion-radicals just at the moment of their formation. These anion-radicals contain the negatively charged oxygen atom. They protonate faster and then undergo dimerization. The resulting hydroxyl-containing carboradicals accept electrons faster and then undergo disproportionation or recombination. This leads to the suppression of ketoenol and pinacol formation. [Pg.353]

The anion-radical mechanism for these syntheses is based on the following facts. The reactions require photo- or electrochemical initiation. Oxygen inhibits the reactions totally, even with photoirradiation. Indoles are formed from o-iodoaniline only the meta isomer does not give rise to indole. Hence, the alternative aryne mechanism (cine-substitution) is not valid. What remains as a question is the validity of the ion-radical mechanism exclusively to the substitution of the acetonyl group for the halogen atom in o-haloareneamine or also for intramolecular condensation. [Pg.374]


See other pages where Atomic Oxygen Anion-Radical is mentioned: [Pg.13]    [Pg.379]    [Pg.150]    [Pg.252]    [Pg.285]    [Pg.122]    [Pg.149]    [Pg.24]    [Pg.61]    [Pg.239]    [Pg.434]    [Pg.202]    [Pg.298]    [Pg.107]    [Pg.185]    [Pg.5]    [Pg.15]    [Pg.57]    [Pg.58]    [Pg.58]    [Pg.58]    [Pg.63]    [Pg.86]    [Pg.170]    [Pg.174]    [Pg.176]    [Pg.195]    [Pg.308]    [Pg.356]    [Pg.63]    [Pg.335]    [Pg.277]    [Pg.102]    [Pg.15]    [Pg.82]    [Pg.1186]    [Pg.209]    [Pg.332]    [Pg.333]    [Pg.364]   
See also in sourсe #XX -- [ Pg.58 ]




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Atomic oxygen anion

Oxygen anion

Oxygen atom

Oxygen atomic

Oxygen radical anion

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