Nitrate reaction with solvated electron

Many of the fast chemical reactions discussed in the preceding sections involve at least one reactant which is of low symmetry. The reactions of the solvated electron with nitrate, naphthalene or pyrene are instances where the oxidant has a mirror plane (in the molecular plane) in the accepting orbital. Hence, reaction of the solvated electron with such a scavenger when both are contained in this plane should be slower than in other configurations. Similarly, the contact quenching of fluorescence from naphthalene or 1,2-benzanthracene by carbon tetrabromide [7], or... 

Even though the reaction conditions may lead to formation of the metal enolate in high yield, further reduction may occur during the quenching step of the reaction. Alcohols such as methanol and ethanol convert metal enolates to saturated ketones much faster than they react with metals in ammonia, and quenching of reduction mixtures with these alcohols will usually lead to partial or complete conversion to alcoholic product rather than to the saturated ketone. Rapid addition of excess solid ammonium chloride is the commonly employed quench procedure if ketonic products are desired,but other reagents that destroy solvated electrons before neutralization may be employed, such as sodium ben-zoate, iron(III) nitrate, - sodium nitrite, bromobenzene, sodium bromate, 1,2-dibromoethane and acetone. 

Cation-radicals of naphthalene and its homologues, pyrene, or perylene react with NOj" ion in AN, giving electron-transfer products, that is, ArH and NOj. The latter radical is not very active in these reactions and nitration takes place only with extremely reactive compounds such as perylene (Eberson and Radner 1985, 1986). This mechanism is seemingly distinctive of compounds with E° less or equal to 1 V in AN (or in other solvents solvating NOj ions sparingly). 

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