Wednesday, 2 December 2015

organic chemistry - Why do larger alkyl groups show a greater inductive (+I) effect?


I have been taught that an alkyl group shows a +I (positive inductive) effect. Why do they do so? I know that hyperconjugation can explain how alkyl groups could stabilize a carbocation (better than a hydrogen). But, how does a longer chain alkyl group (or a bulkier alkyl group) show more +I effect than a smaller one?



Answer



Qualitatively:


If a methyl group is more electron donating than a hydrogen, then an ethyl group would be more donating that a methyl group by the same reason.



The effect drops off with distance, and generally a pentyl group is considered no more donating than a butyl group.


As for why a methyl group is more electron donating than a hydrogen, the carbon has a higher electronegativity than hydrogen (slightly), polarizing the bond (slightly). This increased electron density near the carbon, which increases (slightly) its electron donation (I+) ability.


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