Abstract
Whereas TeCl4 and SnCl4 form 1 : 1 adducts with nitroanilines in dioxan solution, ZrBr4 forms 2acid: 1 base adducts in which both the amino- and the nitro-group of the base are probably involved. The strengths of the acids, judged by the values of K1,1 for 1 : 1 adduct formation and by the concentration of acid required to convert the base into the adduct, follow the sequence ZrBr4 > TeCl4 > SnCl4, and it can also be concluded that the sequence ZrCl4 TelCl4 > SnCl4 obtains. This sequence supports our earlier predictions concerning the effects of the electronic structure of the metal atom on the acidity of covalent halides. Adduct formation between SnCl4 and a serIes of unhindered anilines in dioxan solution is related to the protonation of the bases by the equation pK1,1=–0.96pKa–0.21, Although p-nitro-substitution provides anomalous high K1,1 values. This result is discussed. Toward anilines SnCl4 provides slightly more acidic solutions in dioxan than in diethyl ether.
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