Electron-transfer processes: peroxydisulfate, a useful and versatile reagent in organic chemistry

Abstract

A review with >40 refs

Using Minisci Reaction for Modification of the tris-Dioximate Metal Clathrochelates: Free-Radical Substitution at the Glyoximate Fragment of an Iron(II)-Encapsulating Cage Framework

“…Indeed, the chlorine atom, being a good leaving group, detaches from this intermediate giving the clathrochelate product FeBd 2 (ClGm(diox))(BF) 2 (Scheme 2,ii). On the contrary, in accordance with the plausible Minisci reaction mechanism, [5] the methine hydrogen atom, that is a much worse leaving group, undergoes oxidation with iron(III) thus leading to the alkylated clathrochelate product FeBd 2 (CH 3 Gm(diox))(BF) 2 and H + . General view of the molecule FeBd 2 (CH 3 Gm(diox))(BF) 2 (single crystal X-ray diffraction analysis, Table 1) is shown in Figure 1.…”

“…On the contrary, in accordance with the plausible Minisci reaction mechanism, [5] the methine hydrogen atom, that is a much worse leaving group, undergoes oxidation with iron(III) thus leading to the alkylated clathrochelate product FeBd 2 (CH 3 Gm(diox))(BF) 2 and H + . General view of the molecule FeBd 2 (CH 3 Gm(diox))(BF) 2 (single crystal X-ray diffraction analysis, Table 1) is shown in Figure 1. The encapsulated iron(II) ion has a distorted trigonal-prismatic (TP) FeN 6 -coordination polyhedron, characteristic of this type of the iron(II) clathrochelates and its average distortion angle j is equal to 23.5° (j=0° for an ideal TP and j=60° for an ideal trigonal antiprism (TAP)).…”

“…Preparation 2 ] (3.48 g, 4.9 mmol) and nitromethane (10 ml) were added to the stirring reaction mixture. This mixture was heated to boiling, BF 3 ·O(C 2 H 5 ) 2 (0.6 ml, 5 mmol) was added and the solvent (23 ml) was partially distilled off for 1.5 h from the boiling reaction mixture (the reaction course was controlled by TLC; eluent: dichloromethane -hexane 1:2 mixture).…”

“…[1] Initially based on an oxidative decarboxylation by persulfate dianion in presence of silver(I) cations as the radical source, further it has been extended to a variety of metal ions [2] and to other radical sources [3][4][5] as well. Different hydroperoxide -Fe…”

On the role of salts for the treatment of wastewaters containing pharmaceuticals by electrochemical oxidation using a boron doped diamond anode

“…3 (b)) and CIP ( Fig. 3 (c) In general, SO 4 À is more likely to participate in electron transfer reactions [49,51,54] than OH which is more likely to participate in hydrogen abstraction or addition reactions [55,56]. The former reactions are selective while the later ones are nonselective.…”