Wednesday, February 15, 2017

organic chemistry - Do lone pairs contribute towards the pi electron count of heterocycles?


I'm not able to understand how the following compounds are aromatic.


When should the lone pairs on heteroatoms be taken into consideration when counting the number of π electrons?


Heterocycles: isoquinoline, thiophene, imidazole, thiazole




Answer



Only count the lone pairs/ pi-bonds/ groups which are participating in conjugation and ignore them in all other cases.


For example, in compound 2 (thiophene), there are two lone pairs on sulfur.


Lone pairs on sulfur in thiophene


One lone pair (brown) is in a p-orbital, and hence participates in conjugation with the two π-bonds. The other lone pair (blue) is pointing outwards from the ring in an $\mathrm{sp^2}$ orbital. This lone pair is orthogonal, or perpendicular, to the π-system and hence cannot take part in conjugation. In total there are six π electrons, and the compound is therefore aromatic.


See also: Conjugated system on Wikipedia.


No comments:

Post a Comment

periodic trends - Comparing radii in lithium, beryllium, magnesium, aluminium and sodium ions

Apparently the of last four, $\ce{Mg^2+}$ is closest in radius to $\ce{Li+}$. Is this true, and if so, why would a whole larger shell ($\ce{...