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I think it's because there has to be 4 C-C connections on the attached group to be able to use the prefix "neo". So if you ignore the hexane and the line connecting the butyl to the hexane, there are only 3 C-C connections (which is why you use the prefix for 3, "tert"), because butyl only has 4 carbons.
You use the prefix neo- when a substitutent has AT LEAST 5 carbons. If the substitutent is composed of fewer than 5 carbons, you cannot use the prefix neo-. Tert-butyl for instance looks similar to neo-(something) in drawings, but due to the number of carbons, you wouldn't use neo-.
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