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Synthesis and Application of a Perfluorinated Ammoniumyl Radical Cation as a Very Strong Deelectronator.

ABSTRACT: The perfluorinated dihydrophenazine derivative (perfluoro-5,10-bis(perfluorophenyl)-5,10-dihydrophenazine) ("phenazineF ") can be easily transformed to a stable and weighable radical cation salt by deelectronation (i.e. oxidation) with Ag[Al(ORF )4 ]/ Br2 mixtures (RF =C(CF3 )3 ). As an innocent deelectronator it has a strong and fully reversible half-wave potential versus Fc+ /Fc in the coordinating solvent MeCN (E°'=1.21 V), but also in almost non-coordinating oDFB (=1,2-F2 C6 H4 ; E°'=1.29 V). It allows for the deelectronation of [FeIII Cp*2 ]+ to [FeIV (CO)Cp*2 ]2+ and [FeIV (CN-t Bu)Cp*2 ]2+ in common laboratory solvents and is compatible with good σ-donor ligands, such as L=trispyrazolylmethane, to generate novel [M(L)x ]n+ complex salts from the respective elemental metals.

SUBMITTER: Schorpp M

PROVIDER: S-EPMC7317951 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Synthesis and Characterization of Stable Iron Pentacarbonyl Radical Cation Salts.

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Project description:Electrochemical or photochemical single-electron oxidation of bench-stable substrates can generate radical cations that offer unique reactivities as intermediates in various bond-formation processes. Such intermediates can potentially take part in both radical and ionic bond formation; however, the mechanisms involved are complicated and not fully understood. Herein, we report electrochemical radical cation aza-Wacker cyclizations under acidic conditions, which are expected to proceed via radical cations generated by single-electron oxidation of alkenes.

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Triarylaminium Radical Cation Promoted Coupling of Catharanthine with Vindoline: Diastereospecific Synthesis of Anhydrovinblastine and Reaction Scope.

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A Manganese(V)-Oxo Tetraamido Macrocyclic Ligand (TAML) Cation Radical Complex: Synthesis, Characterization, and Reactivity Studies.

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Strong Inhibition of O-Atom Transfer Reactivity for Mn(IV)(O)(π-Radical-Cation)(Lewis Acid) versus Mn(V)(O) Porphyrinoid Complexes.

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| S-EPMC4888055 | biostudies-literature

Tunneling in C-H oxidation reactions by an oxoiron(IV) porphyrin radical cation: direct measurements of very large H/D kinetic isotope effects.

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Project description:A method for the study of reactions of open-shell neutrals (radicals) and radical cations is described. Pyrolysis (25-1500 degrees C) of thermally labile compounds, such as, 1,5-hexadiene via a Chen nozzle yields a seeded beam of reactive species in helium. The pyrolysis products are then analyzed by electron ionization (EI) or reacted with stored ions. Electron ionization of the pyrolysis products of 1,5-hexadiene shows that both the allyl radical and allene are generated. Reactions of benzene radical cations and the pyrolysis products of 1,5-hexadiene result in carbon-carbon bond formation. Those reactions of allyl radical with the benzene radical cation yield the C(7)H(7) (+) ion of m/z 91, permitting an unusual entry into arenium ions. The reaction of allene with benzene radical cation in contrast yields C(9)H(10) (+). and C(9)H(9) (+).

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| S-EPMC8757455 | biostudies-literature

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