Redox reactivity

In a study directed to the analysis of the role of Fe and the generation of H2O2 in Escherichia coli (McCormick et al. 1998), hydroxyl radicals were specihcally trapped by reaction with ethanol to give the a-hydroxyethyl radical. This formed a stable adduct with a-(4-pyridyl-l-oxide)-iV-t-butyl nitroxide that was not formed either by superoxide or hydroxyl radicals. The role of redox-reactive iron is to use EPR to analyze the EPR-detectable ascorbyl radicals. 

Recently, it has been demonstrated that coordination vacancies on the surface metal cations are relevant to the unique redox reactivity of oxide surfaces]2]. Oxidation of fonnaldehyde and methyl formate to adsorbed formate intermediates on ZnO(OOOl) and reductive C-C coupling of aliphatic and aromatic aldehydes and cyclic ketones on 1102(001) surfaces reduced by Ar bombardment are observed in temperature-prognunmed desorption(TPD). The thermally reduced 1102(110) surface which is a less heavily damaged surface than that obtained by bombardment and contains Ti cations in the -t-3 and +4 states, still shows activity for the reductive coupling of formaldehyde to form ethene]13]. Interestingly, the catalytic cyclotrimerization of alkynes on TiO2(100) is also traced in UHV conditions, where cation coordination and oxidation states appear to be closely linked to activity and selectivity. The nonpolar Cu20( 111) surface shows a... 

Sample preparation for the common desorption/ionisation (DI) methods varies greatly. Films of solid inorganic or organic samples may be analysed with DI mass spectrometry, but sample preparation as a solution for LSIMS and FAB is far more common. The sample molecules are dissolved in a low-vapour-pressure liquid solvent - usually glycerol or nitrobenzyl alcohol. Other solvents have also been used for more specialised applications. Key requirements for the solvent matrix are sample solubility, low solvent volatility and muted acid - base or redox reactivity. In FAB and LSIMS, the special art of sample preparation in the selection of a solvent matrix, and then manipulation of the mass spectral data afterwards to minimise its contribution, still predominates. Incident particles in FAB and LSIMS are generated in filament ionisation sources or plasma discharge sources. 

Redox Reactivity of Coordinated Ligands in Pentacyano(L)Ferrate Complexes Jose A. Olabe... 

Organic ligands without redox reactivity that coordinate metal oxide surface sites have been found to enhance rates of both reductive and non-reductive dissolution reactions ( 7). ... 

Tetramethyl-l-pyrroline-l-oxide ([11] TMPO) underwent inverted spin trapping but only with one nucleophile, triethyl phosphite. This is expected in view of the even lower redox reactivity of TMPO, E° = 1.8 V. 

The electrochemistry of RH-Nu systems is well established (Eberson and Nyberg, 1976 Eberson et al., 1991 Childs et al., 1991). The radical cation mechanism has been shown to prevail for most situations where Nu = F , Cl-, RCOCT, OCN", CN", NO-r, Py and triethyl phosphite, all of them nucleophiles that are difficult to oxidize (Table 5). The initial formation of Nu" is indicated for the redox-reactive SCN", NJ, I- and N02, with Br and (N02)3C occupying a somewhat indeterminate position. 

Tetrabutylboride ion, Bu4B", is oxidized anodically with pa = 0.35 V and thus combines low nucleophilicity with high redox reactivity. Electrolysis of its... 

Photochemical ET reactions can be classified in at least three categories (which can co-exist), namely (i) simple homolysis of bonds of neutral molecules to give radicals of low redox reactivity (ii) excitation of a species D to produce an excited state D which initiates a second-order ET reaction involving another component of acceptor type, A, with formation of the radical pair D + A (iii) direct excitation of a charge transfer (CT) complex formed between two reaction components D and A to form the same radical pair D + A -. The first case is obviously an ideal situation if it can be realized, but this is seldom the case. The incursion or predominance of situations (ii) and/or (iii) in almost any system is possible, and precautions must be taken to avoid these complications. Much can be done by controlling the wavelength of the light source, but it is also possible to affect the chemistry in a predictable manner. 

Remarkable positive shifts of the °red values of the singlet excited states of the metal ion-carbonyl complexes as compared to those of the triplet excited states of uncomplexed carbonyl compounds (Table 2) result in a significant increase in the redox reactivity of the Lewis acid complexes versus uncomplexed carbonyl compounds in the photoinduced electron-transfer reactions. For example, photoaddition of benzyltrimethylsilane with naphthaldehydes and acetonaphthones proceeds efficiently in the presence of Mg(C104)2 in MeCN, although... 

Trimethylsilyl triflate (McsSiOTf) acts as an even stronger Lewis acid than Sc(OTf)3 in the photoinduced electron-transfer reactions of AcrCO in dichloro-methane. In general, such enhancement of the redox reactivity of the Lewis acid complexes leads to the efficient C—C bond formation between organosilanes and aromatic carbonyl compounds via the Lewis-acid-catalyzed photoinduced electron transfer. Formation of the radical ion pair in photoinduced electron transfer from PhCHiSiMes to the (l-NA) -Mg(C104)2 complex (Scheme 11) and the AcrCO -Sc(OTf)3 complex (Scheme 12) was confirmed by the laser flash experiments [113]. 

Such electrochemical processes can be described on the basis of the model developed by Lovric and Scholz [115, 116] and Oldham [117] for the redox reactivity of nonconducting solids able to be permeated by cations or anions (so-called ion-insertion solids). As described in the most recent version of Schroder et al. [118], the electrochemical process is initiated at the three-phase junction between the electrode, the electrolyte solution, and the solid particle, as schematized in Fig. 2.6. From this point, the reaction expands via charge diffusion across the solid particle. It is assumed that, for a reduction process, there is a flux of electrons through the... 

Wade, R., and Castro, C. (1990). Redox reactivity of iron(lll) porphyrins and heme proteins with nitric oxide. Nitrosyl transfer to carbon, oxygen, nitrogen and sulfur. Chem. Res. Toxicol. 3, 289-291. 

REDOX REACTIVITY OF COORDINATED LIGANDS IN PENTACYANO(L)FERRATE COMPLEXES... 

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