Solvent Effects

Solvation of nucleophilic anions markedly influences their reactivity. The nucleophilicities cited above were obtained from reactions in methanol solution. Polar, protic solvents such as water and alcohols solvate anions by hydrogen bonding interactions, as shown in the diagram on below.

These solvated species are more stable and less reactive than the unsolvated "naked" anions. Polar, aprotic solvents such as DMSO (dimethyl sulfoxide), DMF (dimethylformamide) and acetonitrile do not solvate anions nearly as well as methanol, but provide good solvation of the accompanying cations. Consequently, most of the nucleophiles discussed here react more rapidly in solutions prepared from these solvents. These solvent effects are more pronounced for small basic anions than for large weakly basic anions. Thus, for reaction in DMSO solution we observe the following reactivity order:

Nucleophilicity:   I^(–) < SCN^(–) < Br^(–) < Cl^(–) ≈ N₃^(–) < CH₃CO₂ ^(–) < CN^(–) ≈ CH₃S^(–) < CH₃O^(–)

Note that this order is roughly the order of increasing basicity.

مواضيع ذات صلة

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Molecular orbitals and aromaticity

The π molecular orbitals of other conjugated cyclic hydrocarbons

Benzene has six π molecular orbitals

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Heats of hydrogenation of benzene and cyclooctatetraene

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Aromaticity

Conjugation and reactivity: looking forward to Chapter 10

The amide group