Unexpected single electron transfer catalysed cyclisation of prenyl sulphone dimer. Evidence for radical anion coupling in the outer-sphere oxidation of prenyl sulphone carbanion

1989 ◽  
pp. 1543 ◽  
Author(s):  
Christian Amatore ◽  
Andr� Thiebault ◽  
Jean-No�l Verpeaux
Keyword(s):  
Electron Transfer ◽  
Radical Anion ◽  
Outer Sphere ◽  
Single Electron ◽  
Single Electron Transfer

Elektronentransfer und Ionenpaare, 15 [ 1– 3] Radikalanion und Radikal-Kontakt-Ionenpaare von Dimesityl-tetraketon / Electron Transfer and Ion Pairing, 15 [1-3] Radical Anion and Radical Ion Pairs of Dimesityl Tetraketone

1990 ◽  
Vol 45 (8) ◽  
pp. 1197-1204 ◽  
Author(s):  
H. Bock ◽  
P. Hänel ◽  
H.-F. Herrmann
Keyword(s):  
Electron Transfer ◽  
Radical Anion ◽  
Ion Pairs ◽  
Ion Pairing ◽  
Single Electron ◽  
Single Electron Transfer ◽  
Temperature Dependent ◽  
Contact Ion Pairs

The radical anion of dimesityltetraketone (ERed, I = -0.40 V) is easily generated in THF by potassium mirror/[2.2.2]-cryptand reduction. Its contact ion pairs with Na⊕, Cs⊕ and Ba⊕⊕ counter cations, prepared in THF solution by single electron transfer from the respective metals, are characterized by their ESR/ENDOR spectra, which exhibit temperature-dependent metal couplings of aNa⊕ = 0.061 mT (190 K), aCs⊕ = 0.021 mT (190 K), and aBa⊕⊕ = 0.145 mT (295 K).

scholarly journals Computational Characterization of Single-Electron Transfer Steps in Water Oxidation

Inorganics ◽  
2019 ◽  
Vol 7 (3) ◽  
pp. 32 ◽  
Author(s):  
Adiran de Aguirre ◽  
Ignacio Funes-Ardoiz ◽  
Feliu Maseras
Keyword(s):  
Electron Transfer ◽  
Water Oxidation ◽  
Density Functional ◽  
Outer Sphere ◽  
Oxidation Catalysis ◽  
Single Electron ◽  
Single Electron Transfer ◽  
Inner Sphere ◽  
Water Oxidation Catalysis

The presence of single-electron transfer (SET) steps in water oxidation processes catalyzed by first-row transition metal complexes has been recently recognized, but the computational characterization of this type of process is not trivial. We report a systematic theoretical study based on density functional theory (DFT) calculations on the reactivity of a specific copper complex active in water oxidation that reacts through two consecutive single-electron transfers. Both inner-sphere (through transition state location) and outer-sphere (through Marcus theory) mechanisms are analyzed. The first electron transfer is found to operate through outer-sphere, and the second one through inner-sphere. The current work proposes a scheme for the systematic study of single-electron transfer in water oxidation catalysis and beyond.

Reductive Outer-Sphere Single Electron Transfer Is an Exception Rather than the Rule in Natural and Engineered Chlorinated Ethene Dehalogenation

2017 ◽  
Vol 51 (17) ◽  
pp. 9663-9673 ◽  
Author(s):  
Benjamin Heckel ◽  
Stefan Cretnik ◽  
Sarah Kliegman ◽  
Orfan Shouakar-Stash ◽  
Kristopher McNeill ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Outer Sphere ◽  
Single Electron ◽  
Single Electron Transfer ◽  
Chlorinated Ethene

Formation of Carbanions from Carboxylate Ions Bearing Electron-Withdrawing Groups via Photoinduced Decarboxylation: Addition of Generated Carbanions to Benzaldehyde

2015 ◽  
Vol 68 (11) ◽  
pp. 1668 ◽  
Author(s):  
Yuta Kumagai ◽  
Takashi Naoe ◽  
Keisuke Nishikawa ◽  
Kazuyuki Osaka ◽  
Toshio Morita ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Electron Acceptor ◽  
Radical Anion ◽  
Single Electron ◽  
Single Electron Transfer ◽  
Mild Conditions ◽  
Efficient Generation ◽  
Photochemical Method

The photoinduced decarboxylation of carboxylate ions bearing electron-withdrawing groups using biphenyl and 1,4-dicyanonaphthalene leads to the efficient generation of carbanions under mild conditions. The efficiency of the carbanion generation is strongly dependent on the single-electron transfer from the photogenerated radical anion of the electron-acceptor to the radical. In particular, the cyanomethyl anion formed using this photochemical method can be added to benzaldehydes to give the corresponding adducts.

scholarly journals The special role of B(C6F5)3 in the single electron reduction of quinones by radicals

2018 ◽  
Vol 9 (41) ◽  
pp. 8011-8018 ◽  
Author(s):  
Xin Tao ◽  
Constantin G. Daniliuc ◽  
Robert Knitsch ◽  
Michael Ryan Hansen ◽  
Hellmut Eckert ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Radical Anion ◽  
Single Electron ◽  
Special Role ◽  
Single Electron Transfer ◽  
Electron Reduction ◽  
Trityl Cation

In the presence of two molar equiv. of B(C6F5)3p-benzoquinone reacts with persistent radicals TEMPO, trityl or decamethylferrocene by single electron transfer to give the doubly O-borylated benzosemiquinone radical anion with TEMPO+, trityl cation or ferrocenium counter cations.

Reversal of Polarity by Catalytic SET Oxidation: Synthesis of Azabicyclo[m.n.o]alkanes via Chemoselective Reduction of Amidines

2021 ◽  
Author(s):  
Sundarababu Baskaran ◽  
Kirana D V ◽  
Kanak Kanti Das
Keyword(s):  
Electron Transfer ◽  
Stereoselective Synthesis ◽  
Single Electron ◽  
Single Electron Transfer ◽  
Catalytic Method ◽  
One Pot ◽  
Oxidative System ◽  
Oxidation Synthesis

A one-pot catalytic method has been developed for the stereoselective synthesis of cyclopropane-fused cyclic amidines using CuBr2/K2S2O8 as an efficient single electron transfer (SET) oxidative system. The generality of this...

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