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The C2 carbon of 2-methyl-1-butene is an sp2 configuration: It is connected to a methyl group and to the rest of the skeleton chain. There is a dipole generated from both of the sp3 carbons towards the C2 carbon, mainly due to the difference in sigma bond strengths. Sigma bonds are stronger than pi bonds, making it slightly more electron pulling. So, having a higher "s" character in sp2 (33% s) will pull dipoles of sp3 (25% s).

There is no dipole generated between a hydrogen and an sp2 carbon. The net dipole strength is therefore stronger in 2-methyl-1-butene than 1-pentene. Since boiling points depend on dipole and London forces, 2-methyl-1-butene will bind better to each other than 1-pentene, thus will have a higher boiling point.

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