Electron Transfer Reactions in Organic Chemistry. V. Examination of Postulated Electron Transfer Processes Involving Anionic and Carbanionic Nucleophiles with the Aid of the Marcus Theory.

The Reaction of the [CpFe(CO)2]− Anion with Pentafluorochlorobenzene: Nucleophilic Aromatic Substitution by Halogen-Metal Exchange

“…) calculated from Eberson formulae based on Marcus ± Hush theory [24] is strongly underestimated, as the reaction happens within the time of mixing even at À 100 8C.…”

Electrochemistry of Organomagnesium Compounds

“…The corresponding bond dissociation energies, D(R−MgBr), for a C−Mg bond obtained from thermochemical measurements 54 are given in Table 8 as well. A linear plot of E o against D(R−MgBr) was reported by Holm 55 and a plot of E o against E d was reported by Eberson 56 , but they did not use these relationships to elucidate the electrochemical process.…”

“…The deposition of Mg at high current efficiency is possible 100 from solutions in THF of aminomagnesium halides, like (N-methylaniline)MgCl, but much better was the solution of magnesium dibutyldiphenylborate, Mg(BBu 2 Ph 2 ) 2 (56) in THF, even without the addition of other organomagnesium compounds. By using a solution of 56 in a mixture of THF and DME it was possible to construct 100 and patent 101 the first cell with a magnesium anode which could be discharged and recharged, but only in four cycles.…”

“…Marcus nonlinear plots of the activation barrier against the reaction free-energy change were reported 53 for reactions of a series of 5 with 83 and 84. It was also found on the basis of the Marcus approach that the SET steps are feasible for the reaction of 5-hexenylmagnesium bromide with 3-phenylimido-2-phenyl-3H -indole and with 2-methoxy-1-nitronaphthalene in THF but are not feasible for the reaction of 5b with pyrazine in ethers 56 . However, later investigations 134 on kinetic isotope effects in reactions of 83 with a series of reagents 5 showed different rds steps for different reagents 5, although all the reactions followed the SET mechanism (a different mechanism for 5s was invoked recently 135 ).…”

Investigation of the mechanism of decyanation of 2,2-diphenylpropionitrile induced by LiAlH4

“…28 Eberson estimated the standard potential of AlH 4 Á /AlH 4 À redox couple as E°o x = À(0.1-0.3 V) vs NHE in THF. 29 House discussed possible electron transfer between carbanions and unsaturated carbonyl compounds in terms of the difference in standard electrode potentials. He concluded, that for E°r ed ÀE°o x more positive than À0.4 V (equivalent to DG°`9.2 kcal mol À1 ) electron transfer would be feasible.…”