Ah, this is a classic case of solvent interference! In the gas phase, it's all about the alkyl groups donating electrons, so tertiary amines are most basic. But in water, the bulky tertiary amines struggle to be solvated by hydrogen bonding, so primary amines win. In my lab, we see this all the time when designing drug molecules—the solvent changes everything, just like the same kinnow seed gives different fruit in different soil! You have to consider the full environment, beta.
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