Chlorine redox properties

The consequences of polychlorination of porphyrins on redox properties of complexes has been investigated.1404 The highly chlorinated porphyrin 3-octachloro-/ /c.vo-tetrakis(3,5-dichloro-2,6-dimethoxyphenyl)porphyrin exhibits a substantial anodic shift for reduction of over 0.5 V and a smaller shift for oxidation versus the unchlorinated precursor. Contrastingly, small potential shifts for the octabromo-substituted 5,10,15,20-tetraphenylporphyrinate arise from the dominance of macrocycle ruffling over electronic effects. In the polychloro complex, distortion does not compensate fully for electron-withdrawing effects of the Cl substituents. 

Functionalization can be used to alter the redox properties of the zinc metalloporphyrin the zinc heptanitroporphyrin shows facile reduction to the air-stable 7r-anion radical.768 Modification of the zinc porphyrin at the, 8 position with chlorine or bromine to induce saddling of the... 

The behavior of thiourea towards copper(II)-chloro complexes in acetone exemplifies the major changes in redox properties provoked by back-donation, as copper (I) and free chlorine are produced 50—52). The back-donation of copper(II) towards the sulfur atom of the thiourea ligand leads to a substantial decrease in electron population at the metal ion. Compensation is effected by the exercise of the EA function of copper towards coordinated chlorine until the electronic properties of copper and chloride approach those of copper (I) and chlorine (0) respectively ... 

The chemical nature of P-700 is difficult to establish. The absorption bleachings correspond approximately to the peaks of Chi a. which appears to be virtually the only tetrapyrrolic pigment in purified PS I particles. It has thus been assumed that P-700 is Chi a bound to a protein. A few recent results, however, may require this hypothesis to be refined. An examination of the spectroscopic and redox properties of P-700 led Wasielewski et al. [13] to propose that P-700 could be the enol form of Chi a where enolization was of the keto ester on ring V. This has not been confirmed by chemical extraction. Extraction experiments, however, have evidenced two other chlorophyll derivatives. A species named Chl-RC I has been isolated from PS I, at a nearly 1/1 molar ratio with P-700 and its structure shown to be a chlorinated derivative. It is not yet clear whether Chl-RC I is a native constituent of PS I or an extraction artefact. Chl-RC I has not been obtained in a recent chemical analysis by HPLC, which instead revealed two Chi a per P-700 [14]. 

As deduced from the magnetic balance results commented on above, also confirmed by XAS data (205), the use of chlorine-containing metal precursors may deeply modify the redox properties of ceria. The reversible contribution plays a minor role, thus suggesting that the presence of chlorine heavily disturbs the H2-CeC>2 interaction (209). This has also been confirmed by some volumetric (209) and TPD studies (166), Likewise, the above results show the existence of a new very important contribution to the total reduction degree reached by ceria. It is specifically related to the Cr ions incorporated into the ceria lattice. Though it does not revert on outgassing, no oxygen vacancies would be associated with this third contribution (52,163,193,195). 

Mendeleev s early periodic table placed manganese and chlorine in the same group. Discuss the chemical evidence for these placements, focusing on the oxides of the two elements and their acid-base and redox properties. Is there a connection between the electronic structures of their atoms In what ways are the elements different ... 

Several investigations of the redox properties of various free base hydroporphyrins and their metal derivatives have been reported. As is typical of many porphyrins and metalloporphyrins, these hydroporphyrins generally show two oxidations and one or more reductions. The reversibility of these redox reactions depends on the nature of the hydroporphyrin and its stereochemistry. For example, the cyclic voltammograms of ris-H2(OEC) and frans-H2(OEC) were superficially alike, although substantial differences existed in the stability of the cation radicals and dications of the cis and trans isomers [85]. The first oxidation of rrans-H2(OEC) was reversible whereas ds-H2(OEC) was not reversible. However, the notable features observed in the redox chemistry of hydroporphyrins is the shift of both oxidation and reduction potentials of hydroporphyrins towards more negative values compared to porphyrins, i.e., they are more easier to oxidise and difficult to reduce [78]. A significant trend was observed in the electrochemistry of free base octaethyl- [86, 87] and tetraphenyl [88,89] hydroporphyrins (Table 2). The porphyrin and chlorin of each series... 

In many cases, synthetic iron porphyrins have been investigated primarily as models of hemes in various proteins, but also as potentially useful magnetic materials, or as metal coordination complexes, since the porphyrin Macrocycle often confers upon the metal unique electronic, magnetic, and redox properties see Redox Properties Processed and chemical reactivities that are interesting in their own right. The properties and chemical reactivities of iron porphyrins will be summarized in this article. Iron complexes of related macrocycles, including reduced hemes (chlorins, isobacteriochlorins, etc.)... 

In the present chapter we want to look at certain electrochemical redox reactions occurring at inert electrodes not involved in the reactions stoichiometrically. The reactions to be considered are the change of charge of ions in an electrolyte solution, the evolution and ionization of hydrogen, oxygen, and chlorine, the oxidation and reduction of organic compounds, and the like. The rates of these reactions, often also their direction, depend on the catalytic properties of the electrode employed (discussed in greater detail in Chapter 28). It is for this reason that these reactions are sometimes called electrocatalytic. For each of the examples, we point out its practical value at present and in the future and provide certain kinetic and mechanistic details. Some catalytic features are also discussed. 

Persson A process for making chlorine dioxide by reducing sodium chlorate with chromium (III) in the presence of sulfuric acid. The chromium (III) becomes oxidized to chromium (VI) and is then reduced back to chromium (III) with sulfur dioxide. This cyclic redox process with chromium avoids complications that would occur if sulfur dioxide itself were used as the reductant. Installed at the Stora Kopparbergs paper mill, Sweden, in 1946. Sheltmire, W. H., in Chlorine, its Manufacture, Properties and Uses, Sconce, J. S., Ed., Reinhold Publishing, New York, 1962,275,538. 

The most common valence state of indium is +3. However, +2 and -i-l valence states also exist. Chemical properties of indium are similar to aluminum. Its redox potential is -0.34V. When heated with chlorine at 200°C, indium becomes a dichloride ... 

The halogens and their oxyacids, particularly chlorine and hypochlorous acid, are widely used as oxidizing and bleaching agents. These properties are related to the variations of redox potentials.17... 

Section 4.3.2 will be devoted to the chemical characterisation studies. Because of the relationship existing between the support reduction degree and the occurrence of the deactivation phenomena mentioned above, we shall review first some of the major problems to be faced in relation to the redox characterisation of ceria and related oxide supports, sub-section 4.3.2.1. Then, we shall discuss the chemisorptive properties of these catalysts. In particular, section 4.3.2.2, will be devoted to the adsorption of H2 and CO, by far the two most commonly used probe molecules. Special attention will be paid to the relationship existing between chemisorptive behaviour and reduction temperature. We shall also report on some recent hydrogen chemisorption studies, in accordance with which, the sensitivity to the deactivation phenomena may vary from one noble metal to the other (97,117,235), being also influenced by the presence of chlorine in the support (163). 

The redox chemistry of chlorine (hydrolysis and disproportionation of CI2 and acid-base properties of HOCl) was reviewed in Section 8.2 (see Figure 8.5). 

Copper(I) complexes catalyse a variety of organic reactions which are of synthetic and industrial importance.305 In such processes that involve halide abstraction from aryl or alkyl halides, the abstraction step by a Cu(I) catalyst is believed to be the rate-determining step. In order to circumvent the property of facile disproportionation of Cu, various methods of stabilising Cu(I) and influencing reaction rates were considered.306 A kinetics study of ligand (L) effects on the reactivity of Cu(I)L complexes towards C13CC02 was undertaken. The results indicated that the rate of the chlorine abstraction reaction was affected by several factors. These were the redox potential of the Cu(II/I)L couple, the hybridisation on Cu(I) in the Cu(I)L complex, steric hindrance, and electron density on the central Cu(I) cation at the binding site of the chlorine atom to be abstracted. The volume of activation,... 

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