Elektronen‐ und Ladungsübertragung: Zur Vereinheitlichung der Mechanismen organischer und metallorganischer Reaktionen

Dirhodium Catalysts That Bear Redox Noninnocent Chelating Dicarboxylate Ligands and Their Performance in Intra‐ and Intermolecular C–H Amination

“…The ligands L1 {2‐[3‐(1‐carboxy‐1‐methylethoxy)phenoxy]‐2‐methylpropanoate}and L2 [(3‐methoxycarbonyl‐2,5‐di‐ tert ‐butylphenoxy)ethanoate] (previously reported in the context of metallomacrocycle assembly)7 have the same backbone chain‐length as esp; however, the backbones of L1 and L2 contain a redox‐active resorcinol‐derived component (Scheme ). Like the more well‐known 1,2‐ or 1,4‐dialkoxy‐substituted benzenes,8 1,3‐dialkoxybenzenes may be oxidized to the corresponding radical cations, as shown in Scheme 9. The meta ‐disubstituted radical species are significantly less stable than their ortho or para congeners 9,10.…”

Calculated One-Electron Reduction Potentials and Solvation Structures for Selected p-Benzoquinones in Water

“…3,7 In organic chemistry, even the classical S N 2, Diels-Alder, and electrophilic aromatic substitution reactions have recently been cast in terms of single electron transfer events. 8,9 Despite the importance of ET, calculating the free energy (alternatively, the reduction potential) for one-electron reductions remains a challenging problem that requires accurately modeling energy changes due to changes in intramolecular bonding and changes in molecular solvation. A variety of methods have been proposed to address these and related issues, ranging from empirical correlations between gas-phase electron affinities and reduction potentials in aprotic solvents [10][11][12] to more general methods of ab initio molecular dynamics calculations.…”

“…Its importance transcends electrochemistry , and encompasses organic, inorganic, and biochemical reactions , Early studies of ET concerned the oxidation−reduction chemistry of metal complexes so that ET now occupies a prominent place in the literature of inorganic chemistry. , In organic chemistry, even the classical S N 2, Diels−Alder, and electrophilic aromatic substitution reactions have recently been cast in terms of single electron transfer events. , …”

Fluorination with XeF2.144. Effect of Geometry and Heteroatom on the Regioselectivity of Fluorine Introduction into an Aromatic Ring

“…Nitration of monosubstituted aromatic molecules has been extensively studied, and the formation of ion radicals as intermediates has been suggested. [34][35][36][37][38][39][40] Similarity in the regioselectivity of nitration and XeF 2 functionalization of studied aromatic molecules supported the formation of ion radicals, which were also observed in the fluorination of some aromatic molecules. 7,8…”

“…Free radical type of functionalization is less probable due to the absence of fluorine attack at position 4, which is characteristic of radical attack, as in photochemically initiated cyanation 23 with ICN where almost equal amounts of four substituted products were observed (Table , entry 10). Nitration of monosubstituted aromatic molecules has been extensively studied, and the formation of ion radicals as intermediates has been suggested. − Similarity in the regioselectivity of nitration and XeF 2 functionalization of studied aromatic molecules supported the formation of ion radicals, which were also observed in the fluorination of some aromatic molecules. , …”