1. Advantages of Chemical Redox Agents 878 2. Disadvantages of Chemical Redox Agents 879 C. Potentials in Nonaqueous Solvents 879 D. Reversible vs Irreversible ET Reagents 879 E. Categorization of Reagent Strength 881 II. Oxidants 881 A. Inorganic 881 1. Metal and Metal Complex Oxidants 881 2. Main Group Oxidants 887 B. Organic 891 1. Radical Cations 891 2. Carbocations 893 3. Cyanocarbons and Related Electron-Rich Compounds 894

/pdf/chemical-redox-agents-for-organometallic-chemistry-4fs84ntwp8.pdf

Chemical Redox Agents for Organometallic Chemistry

Ruthenium-Catalyzed Reactions for Organic Synthesis.

Human paraoxonases (pon1, pon2, and pon3) are lactonases with overlapping and distinct substrate specificities

Molecular Rods. 1. Simple Axial Rods.

: A mechanism for thermal production of excited states is discussed. Electron transfer from an easily oxidized donor to a suitable organic peroxide followed by oxygen-oxygen bond cleavage generates radical ion intermediates. Subsequent chemical reaction followed by charge annihilation generates electronically excitated state products. This sequence of reactions is called chemically initiated electron-exchange luminescence and is shown to be operating for diphenoyl peroxide, 1-phenylethylperoxy acetate, dimethyldioxeta-none, and 1,4-diphenyl-2,3-benzodioxin (0-xylylene peroxide). (Author)

Chemiluminescence of organic peroxides. Conversion of ground-state reactants to excited-state products by the chemically initiated electron-exchange luminescence mechanism

The chemcial mechanism for formatin of electronically excited-state molecules from the thermal reaction of dimethyldioxetanone was studied. Light production in the presence of certain easily oxidized aromatic hydrocarbons was found not to conform to the classical mechanistic schemes for chemiexcitation. Detailed investigation of the dioxetanone system revealed light formation by the recently discovered, chemically initiated electron-exchange process. This result is extrapolated to bioluminescent systems. In particular, the key high-energy molecule involved in firefly luminescence, which has been identified as a dioxetanone, is postulated to form excited states as a result of intramolecular electron transfer from the phenoxythiazole moiety to the dioxetanone. Subsequent rapid decarboxylation results in direct formation of an excited single state of the emitting amide.

https://www.pnas.org/content/pnas/75/1/30.full.pdf

Bioluminescence of the firefly: key steps in the formation of the electronically excited state for model systems

: Dimethyldioxetanone (2a) undergoes two distinct thermal reactions which generate electronically excited states. The unimolecular decomposition of 2a at 30.0 C produces excited singlet and triplet acetone, with efficiencies of 0.1 and 1.5% respectively. The composite activation energy for formation of singlet acetone is 3-4 kcal/mol greater than the activation energy for the thermal disappearance of 2a. This result is interpreted in terms of two parallel competitive pathways for dioxetanone decomposition, the more highly activated one of which leads to excited acetone. The addition of easily oxidized aromatic hydrocarbons or amines catalyzes the chemiluminescence of 2a. The magnitude of the catalytic rate constant, and the efficiency of light production are correlated with the one electron oxidation potential of the hydrocarbon. Under these conditions the chemiluminescence results from a chemically initiated electron-exchange luminescence (CIEEL) path. (Author)

Chemiluminescence of dimethyldioxetanone. Unimolecular generation of excited singlet and triplet acetone. Chemically initiated electron-exchange luminescence, the primary light generating reaction

Preparation des complexes qui perdent leur coordinat triflate quand ils sont attaques par les nucleophiles. Stœchiometrie des reactions de substitution par THF, acetone, ether, CH 3 CN et P(n-Bu) 3 . Cinetique et parametres d'activation

Properties of (trifluoromethanesulfonato)pentacarbonylmanganese(I) and -rhenium(I). Reactions in superacid solvents

: The chemiluminescence of dimethyldioxetanone (1) in the presence of easily oxidized aromatic hydrocarbons was studied. It was observed that the rate of reaction of (1) depends upon the nature and concentration of the aromatic hydrocarbon. The efficiency of light production was correlated with the one electron oxidation potential of the hydrocarbon. These results are interpreted in terms of the recently described chemically initiated electron exchange luminescence. (Author)

Steven P. Schmidt

Papers

Bioluminescence of the firefly: key steps in the formation of the electronically excited state for model systems

Chemiluminescence of dimethyldioxetanone. Unimolecular generation of excited singlet and triplet acetone. Chemically initiated electron-exchange luminescence, the primary light generating reaction

Properties of (trifluoromethanesulfonato)pentacarbonylmanganese(I) and -rhenium(I). Reactions in superacid solvents

Dioxetanone chemiluminescence by the chemically initiated electron exchange pathway. Efficient generation of excited singlet states

Rod-like organic molecules. Energy-transfer studies using single-photon counting