Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases p. 589 - 598 (1983)
Update date:2022-09-26
Topics:
Langan, John R.
Salmon, Arthur G.
Absorption spectra of free-radical anions and their ion pairs with Na+ and Li+ of 1,1-diphenylethylene (D), α-methylstyrene (MS) and styrene(S) were recorded by pulse radiolysis of solutions of the hydrocarbon in either neat tetrahydrofuran or tetrahydrofuran containing sodium or lithium tetrahydrido-aluminate salts.The spectra indicate that radical anions of 1,1-diphenylethylene and α-methylstyrene associate with Na+ and Li+ to give solvent-separated ion pairs; but styrene redical anions form contact ion pairs with Na+.Rates of reaction of eS-, (Na+C,eS-) and (Na+, eS-) with these hydrocarbons and with pyrene and biphenyl were determined and were found to follow the order eS- > (Na+C,eS-) > (Na+,eS-) for each solute.Except for 1,1-diphenylethylene, the reactivity of (Na+,eS-) with these and some related hydrocarbons was found to increase slightly with the electron affinity of the hydrocarbon.The rates of dimerization of the redical anions of D, MS and S have been determined and the influence of ion pairing with Na+ and Li+ has been studied.The dimerization rates of (Na+,MS.-), (Li+,MS.-) and (Na+C,MS.-) are 6.6E8, 1.23E9 and 6.42E9 dm3 mol-1 s-1, respectively, and the latter value was found to be independent of ionic strength.Absorption spectra of the dimer dianions of D and MS were also recorded.
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