Reaction of hydrated electrons with guanine derivatives: tautomerism of intermediate species.

Here, we show that two tautomers are produced by the protonation of the guanine-electron adduct. The fate of electron adducts of a variety of substituted guanosines was investigated by radiolytic methods and addressed computationally by means of time-dependent DFT (TD-B3LYP/6-311G**//B1B95/6-31+G**) calculations. The reaction of e aq - with guanosine and 1-methylguanosine produces two transient species, whereas the reaction with N 2 -ethylguanosine and N 2 ,N 2 -diethylguanosine produces only one. The two short-lived intermediates, which show a substantial difference in their UV-visible spectra, are recognized to be two purine tautomers (i.e., iminic 18 and aminic 19 forms). The tautomerization 18 → 19 occurs with a rate constant of ca. 1.5 x 10 6 s -1 , and theory suggests that it is a water-assisted process.