Experimental Theoretical Impulse Constants

TABLE 1 Comparison of Experimental Theoretical Impulse Constants... 

Thus, the calculations [13] have produced evidence in favor of the Kornblum-Russell mechanism elucidating certain details of the nature and structural conditions for realization of its individual steps. Of course, so far only the simplest models have been considered, and the effect of the simplifying assumptions may in some cases be quite substantial. For example, experimental studies of radical-anions of various halogennitrobenzyl compounds IV using the impulse radiolysis technique [28] show that, unlike the chloronitromethyl radical considered earlier, the compounds IV do exist in solution for some finite time. Even so, their decomposition is, in accordance with the theoretical prediction, speeded up upon weakening of the C—X bond. The reaction proceeds by the scheme of intramolecular, inner-sphere electron transfer whose relatively low rate constant (10 -10 s) can be accounted for by the small overlap of the Ti-orbital, which carries the unpaired electron in the initial form IV and is localized predominantly at the nitro group, and the (j -orbital C—X ... 

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