Tuesday 26 January 2016

organic chemistry - Why is the lone pair of pyridine's nitrogen atom not part of the aromatic ring?



In pyrrole, the lone pair of electrons belonging to the nitrogen is part of the aromatic ring. However, in pyridine it is part of an sp2-hybridized orbital. Why can't it be in the p-orbital and take part in the aromatic ring?


I mean, why can't the lone pair in pyrrole be in the p-orbital, with the sp2-hybridized orbital (which is not bonded to anything) sporting a single electron?


I'm not talking about the nitrogen atom having two p-orbitals participating in the aromatic ring. That would be strange. I wonder why the existing p-orbital of N cannot carry two electrons, the way it does in pyrrole.


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P.S. A related question, with a very interesting answer: sp2-hybpidization in pyridine and pyrrole



Answer



As follows from our discussion in the comments to the question, pyridine uses only a single electron in the p-orbital in order to comply with Huckel's rule. Kudos to Orthocresol:



Huckel's rule demands that there be 4n+2 pi electrons in the ring. Each carbon contributes one, making for a total of 5 from the carbons. If your nitrogen lone pair is in the ring, then you will have seven pi electrons. $7≠4n+27≠4n+2$ for $n ∈Z$




Of course, electrons know nothing of Huckel and his rule, but apparently they position themselves into the most energetically suitable configuration. I am not yet qualified to explain why exactly it is the most suitable one.


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