Substituent Effects in Phenoxide and Anilide Anions

In the discussion up till now, we have only considered interactions between neutral substituents. This section details substituent interactions with two negatively charged groups, 0 and NH , and examines also the differences between these two groups. Total and relative energies for substituted phenoxide and anilide ions are listed in Tables 17 and 18. Interaction energies are presented in Table 19, together with those for anilinium ions, which are discussed subsequently (Section V.E). 

From the charge data for monosubstituted benzenes (Table 2), it can be seen that both O and NH are powerful tt donors and poor a donors. The deprotonation of phenol to yield phenoxide has the effect of raising all the orbitals associated with the O atom, including those orthogonal to the orbitals responsible 

Substituent (X) Conformation Total energy (hartrees) Relative energy (kcal mole ) 

Interaction Energies (kcal mole ) for Substituted Phenoxide, Anilide, and Anilinium Ions 

Substituent (X) Phenoxide anion Anilide anion Anilinium cation  

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