The OpenSMILES aromaticity challenge...

I think I've identified a fundamental problem with all of the OpenSMILES 
aromaticity discussions so far.  People keep sending examples where a 
particular atom "donates 1 or 2 electrons," or "can donate 1 electron."  I 
think that's completely bogus.  If you don't know whether it's 0, 1 or 2, then 
you haven't specified the atom's environment well enough.

A perfect example of this is OpenBabel itself.  The original aromaticity rules 
have a *range* of electrons that can be donated by the atom matched by a 
particular SMARTS.  And in every case, if you do a bit of investigation, you 
can split the rule into two new rules, each with a more specific SMARTS, where 
there's no ambiguity any more.

So here is the challenge: Can you identify an aromatic atom where the number of 
electrons it donates is ambiguous, and there is no reasonable SMARTS that can 
separate the two cases?  I'm going to claim that there are *no* situations 
where we don't know exactly the number of electrons each atom will donate, if 
we specify a precise enough SMARTS.

(This is trivially true in the sense that you could write the SMARTS of every 
possible aromatic ring system, but I'm not talking about that.  I'm talking 
about a sensible SMARTS that defines one atom's immediate environment, in most 
cases its nearest neighbors but in a few cases perhaps you need to go two 
neighbors out.)

The OpenSMILES page has an enumeration of atoms that could be aromatic that you 
might use as a starting point.  Are there others?

http://www.opensmiles.org/spec/open-smiles-3-input.html#3.5.3

I'm sending a copy of this email to the OpenBabel list too.  I'll wait a week 
or so for replies and then post a summary to the BlueObelisk-SMILES discussion.

Craig

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