Redox spectra

Less well-defined redox spectra are obtained for analogous Co3Cp3 complexes, which show two reversible 1 -e oxidation processes at ca. 0.5,0.8 V, separated by ca. 140 mV, again suggesting some electronic communication between the two clusters. Attempted chemical oxidation (Ag+) gave unstable uncharacterized pale yellow compounds. 

The differential redox spectra that the 00 Snal of PS I particles is higher than that of thylakoids and that the P oq signal is lower than that of tyhylakoids. This results showed that the prepared PS I particles are richer in PS I reaction center. 

The electrochemistry of S-N and Se-N heterocycles has been reviewed comprehensively. The emphasis is on the information that electrochemical studies provide about the redox properties of potential neutral conductors. To be useful as a molecular conductor the 4-1, 0, and -1 redox states should be accessible and the neutral radical should lie close to the centre of the redox spectrum. The chalcogen-nitrogen heterocycles that have been studied in most detail from this viewpoint... 

Earlier we described a voltammogram as the electrochemical equivalent of a spectrum in spectroscopy. In this section we consider how quantitative and qualitative information may be extracted from a voltammogram. Quantitative information is obtained by relating current to the concentration of analyte in the bulk solution. Qualitative information is obtained from the voltammogram by extracting the standard-state potential for the redox reaction. For simplicity we only consider voltammograms similar to that shown in Figure 11.33a. 

The initial radicals formed from the Ce(IV) ion redox system can initiate a monomer to polymerize and form an end group of the resulting polymer. When the reductant exhibits a carbonyl group, the amide group can be conveniently detected by the FT-IR spectrum of the polymer, such as polyacrylonitrile (PAN). The FT-... 

The second distinguishing feature of the Rieske protein apart from its unique EPR spectrum that was recognized early is its high redox potential 91). The redox potentials of Rieske clusters from mitochondrial and bacterial bci complexes are in the range of +265 to + 310 mV (Table XI) the potentials in complexes are even slightly... 

The applications of EPR spectroscopy reviewed in the present chapter are based on the sensitivity of the spectrum displayed by iron-sulfur centers to various characteristics, such as the redox state of the center, the distribution of the valences on the iron ions, the nature and the geometry of the ligands, and the presence of nearby paramagnetic species. Although considerable progress has been made during the past few years in the quantitative analysis of these various effects in the case of the conventional iron-sulfur centers described in Section II, the discovery of centers exhibiting unusual EPR properties as... 

After the reaction for 5 h in a reactant stream of CH , O, and Hj (P(CHJ= 33.7, P(0,)= 8.4 and P(H2)= 50.7 kPa), the catalyst was analyzed by XRD, Mossbauer and XPS studies. As regarding the XRD and Mossbauer spectroscopic measurements, obvious changes were not observed before and after the reaction. On the other hand, a marked change was observed in the XPS spectrum of the catalyst after the reaction. As shown in Fig. 2, besides the peak at 57.7 eV, which was the only peak of Fe3p obtained for the sample before the reaction and was ascribed to Fe(III), a clear shoulder at 56.1 eV was observed after the reaction. This can be ascribed to the Fe(ll) on the catalyst surface. The same phenomenon has been reported for FeP04 catalyst [13]. Such observations suggest the occurrence of the redox of iron between Fe(Iil) and Fe(II) during the reaction. We believe that this redox plays a key role in the formation of a new active center and thus is important in the selective oxidation of CH4... 

The nuclear decay of radioactive atoms embedded in a host is known to lead to various chemical and physical after effects such as redox processes, bond rupture, and the formation of metastable states [46], A very successful way of investigating such after effects in solid material exploits the Mossbauer effect and has been termed Mossbauer Emission Spectroscopy (MES) or Mossbauer source experiments [47, 48]. For instance, the electron capture (EC) decay of Co to Fe, denoted Co(EC) Fe, in cobalt- or iron-containing compormds has been widely explored. In such MES experiments, the compormd tmder study is usually labeled with Co and then used as the Mossbauer source versus a single-line absorber material such as K4[Fe(CN)6]. The recorded spectrum yields information on the chemical state of the nucleogenic Fe at ca. 10 s, which is approximately the lifetime of the 14.4 keV metastable nuclear state of Fe after nuclear decay. 

As illustrated in Fig. 9.40, progressively more complex models for the environment of Fe in oxidized or reduced rubredoxin produce better simulations of the NIS pattern. A simple Fe(SCH3)4 model (21 atoms) predicts a division of the spectrum into Fe-S stretch and S-Fe-S/Fe-S-C bend regions, but at least a model with 49 atoms is needed to reproduce the splitting of the stretch region and to capture some of the features between 10 and 30 meV. These results confirm the delocalization of the dynamic properties of the redox-active Fe site far beyond the immediate Fe-S4 coordination sphere. 

The toxicity of 3-methylindole has been attributed to methyleneindolenine trapping of nitrogen and sulfur nucleophiles.57 60-62 Likewise, the ene-imine shown in Scheme 7.9 readily reacted with hydroquinone nucleophiles, resulting in head-to-tail products. Shown in Fig. 7.6 is the 13C-NMR spectrum of a 13C-labeled ene-imine generated by reductive activation. The presence of the methylene center of the ene-imine is apparent at 98 ppm, along with starting material at 58 ppm and an internal redox reaction product at 18 ppm. Thus, the reactive ene-imine actually builds up in solution and can be used as a synthetic reagent. 

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