201135-82-2Relevant academic research and scientific papers
Correlation between the Basicity of Carbanions and Their Ability to Transfer an Electron
Bordwell, Frederick G.,Clemens, Anthony H.
, p. 1035 - 1037 (1981)
In Me2SO solution electron transfer from 9-arylfluorenyl carbanions, 9-ArFl-, to electron acceptors including PhSO2CH2Br, PhSO2CH2I, or R2C(NO2)2 follows second-order kinetics and results in the formation of dimers, (9-ArFl-)2, in high yields.Broensted-type correlations of log k2 vs. pKa (Table I) show that these electron-transfer processes have a much higher sensitivity to changes in 9-ArFl- ion basicity (βNu>1.0) than do SN2 reactions of RX with these carbanions (βNu=0.3-0.5).
Correlation of Electron-Transfer Rate Constants of Carbinons with Their Oxidation Potentials and Basicities
Bordwell, Frederick G.,Bausch, Mark J.
, p. 1985 - 1988 (2007/10/02)
Acidity-oxidation-potential (AOP) values for seven 9-substituted fluorenide ions, 9-ArFl(1-), relative to that of fluorene, have revealed the presence of small radical-stabilizing effects for 4-MeO and 4-Me substitutents in the aryl ring and a 3-Me substituent in the fluorene ring and their absence for 3-Cl and 4-MeSO2 substituents in the aryl ring and 2-Br and 2-PhSO2 substituents in the fluorene ring.Measurements of redox potentials have shown that electron-transfer (eT(1-)) reactions of these 9-ArFl(1-) ions with 1,1-dinitrocyclohexane are endergonic by 6.6-13 kcal/mol.A Bronsted-type plot of log kobsd for these reactions vs. pKHA was linear with scatter.A Bronsted-type plot of log kobsd vs.Eox gave an improved plot (β = 1.04; R2 = 0.999) that covered a rate range of >1E5 and an Eox range of 7.3 kcal/mol.Mechanistic schemes are presented to account for the products formed in the eT(1-) reaction and to reconcile the strict linearity of the latter plot with the Marcus equation.
