Garst

The simple rules refer to nuclear spin selection during mixing of Tq and S states of the radical pair. If mixing of T+j and S states occurs instead, entirely different rules apply as discussed in Section IV (Kaptein, 1971b, 1972a Kaptein and den Hollander, 1972 Garst et al., 1971 J. I. Morris et al, 1972). 

On the basis of reaction-product structures, it might be expected that the reactions of organic halides with sodium naphthalene (Scheme 9) might resemble mechanistically the reactions of organic halides with lithium alkyls. CIDNP studies have shown that they are in fact quite different, in particular in the mechanism by which polarization occurs. The observations are as follows (Garst et al., 1970). 

This type of polarization appears to be general in such systems and it has been proposed that it arises because of T i-S mixing. An interesting and important addif ional observation comes from a study of the reaction of isopropyl chloride with sodium naphthalene in a field of 60 G. Net emission in the products is predicted for T i-S mixing and multiplet polarization for Tq-S mixing. Since no multiplet polarization can be detected, it would seem that Tq-S mixing is suppressed in this system (Garst et al., 1971). Presumably, the naphthalene radical anion... 

Somewhat similar observations have been made in the reaction of alkyl halides with sodium mirrors (the Wurtz reaction) in which alkyl coupling occurs. Thus, ethane formed on treatment of methyl iodide with sodium in a field of 20 G shows n.m.r. emission (Garst and Cox, 1970). The phase is consistent with polarization via T j-S mixing,... 

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