The reactivity of a solvated electron with MgII salts in THF is investigated by pulse radiolysis. With magnesium
chloride, no reaction is observed, but when magnesium perchlorate is used, the solvated electron reacts to
form a species absorbing in the near-infrared. Conductivity measurements show that neither MgCl2 nor Mg(ClO4)2 is dissociated in THF. Quantum chemical calculations show that the difference in behavior between
the two salts can be traced back to the electron affinities of the solutes in the gas phase. The solvated electron
forms a stable pair only with magnesium perchlorate. The structure of this pair is proposed. The rate constants
of the reactions and the extinction coefficients of the different species involved in the formation and decay
of the pair are determined with a probabilistic global analysis method of the time-resolved absorbance signals.
The reactivity of the pair formed by magnesium perchlorate with solvated electron in THF with aromatic
molecules and halogenated hydrocarbons was investigated by pulse radiolysis. The kinetics of electron transfer
from the pair to aromatic molecules with reduction potentials covering a 1 V range were recorded. The
corresponding rate constants were determined and show that the pair presents a strong reducing character
because it can reduce biphenyl which has a low redox potential. Nevertheless, the pair is still a weaker reducing
agent than the solvated electron in THF. Moreover, we estimated the rate constants of the reaction between
the pair and different types of alkyl halogenides.
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