Photoinduced alkylation of five-membered heteroaromatic compounds via electron-transfer reaction: heterodimer cation radical intermediacy

1981 ◽  
Vol 103 (18) ◽  
pp. 5570-5572 ◽  
Author(s):  
Kazuhiko Mizuno ◽  
Masao Ishii ◽  
Yoshio Otsuji
Keyword(s):  
Electron Transfer ◽  
Transfer Reaction ◽  
Cation Radical ◽  
Electron Transfer Reaction ◽  
Heteroaromatic Compounds

Elektronenreiche Olefine, 2 Struktur und Elektrontransfer-Reaktivität des cyclisch σ/π-hyperkonjugierten Carbosilans 3,3,6,6-Tetrakis(trimethylsilyl)-1,4-cyclohexadien

1988 ◽  
Vol 43 (9) ◽  
pp. 1087-1093 ◽  
Author(s):  
Hans-Dieter Hausen ◽  
Christian Bessenbacher ◽  
Wolfgang Kaim
Keyword(s):  
Molecular Structure ◽  
Electron Transfer ◽  
Transfer Reaction ◽  
Crystal And Molecular Structure ◽  
Cation Radical ◽  
Electron Transfer Reaction ◽  
Boat Conformation ◽  
Single Electron Transfer ◽  
Molecular Structure Analysis ◽  
Single Electron Transfer Reaction

Abstract Crystal and molecular structure analysis of the title compound 1, a most electron rich carbosilane, exhibits a shallow boat conformation for the cyclohexadiene ring which is shielded by four bulky Me3Si groups. Multiple hyperconjugative interaction occurs between the two non-conjugated olefinic π systems and the four rather long (192 pm) carbon-silicon o bonds which form an angle of about 34° with the assumed π axis. The HOMO destabilization caused by this unique structural arrangement explains the energetically facile formation and subsequent reactivity of the cation radical 1+ which was found to undergo oxidative desilylation to the aromatic 1,4-bis(trimethylsilyl) benzene precursor in the single electron transfer reaction with TCNE.

scholarly journals Electron transfer studies of a conventional redox probe in human sweat and saliva bio-mimicking conditions

2021 ◽  
Vol 11 (1) ◽  
Author(s):  
P. Krishnaveni ◽  
V. Ganesh
Keyword(s):  
Electron Transfer ◽  
Crystalline Phase ◽  
Liquid Crystalline ◽  
Transfer Reaction ◽  
Electron Transfer Reaction ◽  
Redox Couple ◽  
Liquid Crystalline Phase ◽  
Transfer Reactions ◽  
Redox Probe ◽  
Human Sweat

AbstractModern day hospital treatments aim at developing electrochemical biosensors for early diagnosis of diseases using unconventional human bio-fluids like sweat and saliva by monitoring the electron transfer reactions of target analytes. Such kinds of health care diagnostics primarily avoid the usage of human blood and urine samples. In this context, here we have investigated the electron transfer reaction of a well-known and commonly used redox probe namely, potassium ferro/ferri cyanide by employing artificially simulated bio-mimics of human sweat and saliva as unconventional electrolytes. Typically, electron transfer characteristics of the redox couple, [Fe(CN)6]3−/4− are investigated using electrochemical techniques like cyclic voltammetry and electrochemical impedance spectroscopy. Many different kinetic parameters are determined and compared with the conventional system. In addition, such electron transfer reactions have also been studied using a lyotropic liquid crystalline phase comprising of Triton X-100 and water in which the aqueous phase is replaced with either human sweat or saliva bio-mimics. From these studies, we find out the electron transfer reaction of [Fe(CN)6]3−/4− redox couple is completely diffusion controlled on both Au and Pt disc shaped electrodes in presence of sweat and saliva bio-mimic solutions. Moreover, the reaction is partially blocked by the presence of lyotropic liquid crystalline phase consisting of sweat and saliva bio-mimics indicating the predominant charge transfer controlled process for the redox probe. However, the rate constant values associated with the electron transfer reaction are drastically reduced in presence of liquid crystalline phase. These studies are essentially carried out to assess the effect of sweat and saliva on the electrochemistry of Fe2+/3+ redox couple.

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