11.1.3 Anion radicals by one-electron reduction of hydrocarbons and related compounds: C-protonation

2005 ◽  
pp. 253-258
Author(s):  
J. K. Dohrmann
Keyword(s):  
Electron Reduction ◽  
Related Compounds ◽  
Anion Radicals

One-Electron Reduction of Kinetically Stabilized Dipnictenes:  Synthesis of Dipnictene Anion Radicals

2006 ◽  
Vol 128 (38) ◽  
pp. 12582-12588 ◽  
Author(s):  
Takahiro Sasamori ◽  
Eiko Mieda ◽  
Noriyoshi Nagahora ◽  
Kazunobu Sato ◽  
Daisuke Shiomi ◽  
...  
Keyword(s):  
Electron Reduction ◽  
Anion Radicals

Electrochemical and spectroelectrochemical characterization of Cu(II) and Mn(III) tetrabutano- and tetrabenzoporphyrins containing sterically hindered meso -(2,6-difluorophenyl) substituents in nonaqueous media

2019 ◽  
Vol 23 (09) ◽  
pp. 1057-1071 ◽  
Author(s):  
Liping Wang ◽  
Yuanyuan Fang ◽  
Weijie Xu ◽  
Zhongping Ou ◽  
Karl M. Kadish
Keyword(s):  
Central Metal ◽  
Redox Potentials ◽  
Nonaqueous Media ◽  
The Third ◽  
Sterically Hindered ◽  
Electron Reduction ◽  
The Given ◽  
Spectroelectrochemical Properties ◽  
Anion Radicals

Four tetrabutano and tetrabenzoporphyrins containing sterically hindered meso-(2,6-difluorophenyl) substituents and copper(II) or manganese(III) central metal ions were synthesized and characterized as to their electrochemical and spectroelectrochemical properties in nonaqueous media. The copper(II) derivatives exhibit the expected two one-electron reductions to give [Formula: see text]-anion radicals and dianions in CH2Cl2. Electrochemical and spectroelectrochemical data suggest that a Cu(II) phlorin anion is generated from the doubly reduced Cu(II) butanoporphyrin and it is this species which undergoes the third reduction in pyridine. The first one-electron reduction of the Mn(III) porphyrins is metal-centered to give a Mn(II) compound, while the second and third reductions are macrocycle-centered to give Mn(II) porphyrin [Formula: see text]-anion radicals and dianions in both CH2Cl2 and pyridine. A Mn(II) phlorin anion is also generated from the Mn(II) dianion on the spectroelectrochemical timescale under the given solution conditions. The [Formula: see text],[Formula: see text]-butano and benzo groups have a significant effect on the measured redox potentials. Steric hindrance of the meso-(2,6-difluorophenyl) substituents also has an effect on the potential separation between the first two oxidations of the benzoporphyrins.

One-electron reduction of quinoxaline derivatives and EPR spectra of their anion radicals

1972 ◽  
Vol 5 (6) ◽  
pp. 612-615
Author(s):  
L. L. Gordienko ◽  
Yu. S. Rozum ◽  
A. G. Chukhlantseva ◽  
V. N. Rudenko
Keyword(s):  
Epr Spectra ◽  
Quinoxaline Derivatives ◽  
Electron Reduction ◽  
Anion Radicals

Resonance Raman and absorption properties of Zn(II) and Ni(II) polynitroporphyrins and their chemical reduction products

2007 ◽  
Vol 11 (09) ◽  
pp. 682-690 ◽  
Author(s):  
Sergei N. Terekhov ◽  
Gennadii N. Sinyakov ◽  
Evgeni E. Lobko ◽  
Pierrette Battiony ◽  
Pierre-Yves Turpin ◽  
...  
Keyword(s):  
Steady State ◽  
Chemical Reduction ◽  
Resonance Raman ◽  
Absorption Properties ◽  
Aryl Ring ◽  
Electron Reduction ◽  
The One ◽  
Steady State Absorption ◽  
Excited Resonance ◽  
Anion Radicals

Electron-deficient metallocomplexes of dodeca- and octanitroporphyrins produced by the introduction of 8 β-nitro substituents or 8 β-nitro and a meta-nitro substituent on each meso-aryl ring of Zn (II) and Ni (II) [meso-tetra-(2,6-dichlorophenyl)porphyrin] (Zn8, Ni8 and Zn12, Ni12, respectively) and their air-stable reduced species have been characterized by steady-state absorption and Soret-excited resonance Raman spectroscopies. One-electron reduced species of the metallocomplexes were produced by three different procedures (in deprotonated tetrahydrofuran in air ambient, in tetralhydrofuran with the addition of piperidine in air ambient, and in contact with a sodium mirror under vacuum) and demonstrated similar absorption and RR spectra. It is concluded on the basis of the RR spectra that the one-electron reduction products of the studied polynitrosubstituted metalloporphyrins are π–anion radicals in character.

Electron spin resonance of fluorine-substituted nitro-aromatic anion radicals

1968 ◽  
Vol 46 (24) ◽  
pp. 3847-3856 ◽  
Author(s):  
P. H. H. Fischer ◽  
H. Zimmermann
Keyword(s):  
Electron Spin Resonance ◽  
Electron Spin ◽  
Half Life ◽  
Coupling Constants ◽  
Acetonitrile Solution ◽  
Spin Resonance ◽  
Related Compounds ◽  
Nitro Benzene ◽  
Nitro Aromatic ◽  
Anion Radicals

Electron spin resonance spectra have been observed for anion radicals derived from 2-fluoro-nitro-benzene, 3-fluoro-nitrobenzene, 2,4-difluoro-nitrobenzene, 2,5-difluoro-nitrobenzene, 4-fluoro-2-nitro-phenol, 2-fluoro-6-nitrophenol, and 3-fluoro-6-nitrophenol. All radicals were generated electrolytically in dimethoxyethane/acetonitrile solution, acetonitrile, or dimethylformamide. The radicals are generally quite stable with the exception of those from 2-fluoro-6-nitrophenol and 3-fluoro-6-nitrophenol, the latter decaying with a half-life of approximately 6 min. All spectra can be interpreted completely, and coupling constants are assigned by comparison to related compounds and consistency arguments.

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