Organolanthanide and organoactinide oxidative additions exhibiting enhanced reactivity. 4. Products, stoichiometry, and preliminary kinetic studies of the reaction of (C5Me5)2Sm(II).cntdot.OEt2 and (C5Me5)2Eu(II).cntdot.OEt2 with alkyl and aryl halides. Evidence for the importance of electron transfer in atom-abstraction oxidative additions

1987 ◽  
Vol 6 (6) ◽  
pp. 1356-1358 ◽  
Author(s):  
R. G. Finke ◽  
S. R. Keenan ◽  
D. A. Schiraldi ◽  
P. L. Watson
Keyword(s):  
Electron Transfer ◽  
Kinetic Studies ◽  
Aryl Halides ◽  
Oxidative Additions

Flavin radicals, conformational sampling and robust design principles in interprotein electron transfer: the trimethylamine dehydrogenase-electron-transferring flavoprotein complex

2004 ◽  
Vol 71 ◽  
pp. 1-14
Author(s):  
David Leys ◽  
Jaswir Basran ◽  
François Talfournier ◽  
Kamaldeep K. Chohan ◽  
Andrew W. Munro ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Dimensional Space ◽  
Three Dimensional ◽  
Kinetic Studies ◽  
Molecular Assembly ◽  
Conformational Sampling ◽  
Trimethylamine Dehydrogenase ◽  
Key Residues ◽  
Electron Transferring Flavoprotein ◽  
Electron Transfer Complex

TMADH (trimethylamine dehydrogenase) is a complex iron-sulphur flavoprotein that forms a soluble electron-transfer complex with ETF (electron-transferring flavoprotein). The mechanism of electron transfer between TMADH and ETF has been studied using stopped-flow kinetic and mutagenesis methods, and more recently by X-ray crystallography. Potentiometric methods have also been used to identify key residues involved in the stabilization of the flavin radical semiquinone species in ETF. These studies have demonstrated a key role for 'conformational sampling' in the electron-transfer complex, facilitated by two-site contact of ETF with TMADH. Exploration of three-dimensional space in the complex allows the FAD of ETF to find conformations compatible with enhanced electronic coupling with the 4Fe-4S centre of TMADH. This mechanism of electron transfer provides for a more robust and accessible design principle for interprotein electron transfer compared with simpler models that invoke the collision of redox partners followed by electron transfer. The structure of the TMADH-ETF complex confirms the role of key residues in electron transfer and molecular assembly, originally suggested from detailed kinetic studies in wild-type and mutant complexes, and from molecular modelling.

scholarly journals Intermolecular oxyarylation of olefins with aryl halides and TEMPOH catalyzed by the phenolate anion under visible light

2020 ◽  
Vol 11 (27) ◽  
pp. 6996-7002
Author(s):  
Kangjiang Liang ◽  
Qian Liu ◽  
Lei Shen ◽  
Xipan Li ◽  
Delian Wei ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Visible Light ◽  
Aryl Halides ◽  
Single Electron ◽  
Single Electron Transfer ◽  
Strong Reduction ◽  
Aryl Radicals ◽  
Reduction Potentials

The phenolate anion was developed as a new photocatalyst with strong reduction potentials (−3.16 V vs. SCE) to reduction of aryl halides to aryl radicals through single electron transfer.

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