Bonding, Structure, and Resonance
How To Find The Best Resonance Structure By Applying Electronegativity
Last updated: December 28th, 2022 |
Finding The Best (And Second-Best) Resonance Structures By Applying Electronegativity
The last time I talked about evaluating resonance structures the molecules were, to be honest – pretty simple. Evaluating the resonance structures of ethene, the allyl carbocation, and the allyl carbanion are a pretty far cry from some of the more complicated structures you’ll see in a typical course.
So today let’s get started with how to evaluate non-equivalent resonance structures from pi bonds.
Table of Contents
- Always Break A Pi Bond So As To Put The Electrons On The More Electronegative Atom
- Evaluating The Resonance Structures Of Acetone (Propanone)
- Evaluating The Resonance Structures Of An Imine
- Evaluating The Resonance Structures Of The Acetate Ion
- Apply The Rule Of Electronegativity To Determine The “Second-Best” Resonance Structures For These Molecules
1. Always Break A Pi Bond So As To Put The Electrons On The More Electronegative Atom
So today I thought I’d start to talk about the (much more common) situation when you have a π bond between two dissimilar atoms. How do you evaluate the resonance forms in these cases?
We’re going to have to go back to using our old friendly measuring stick, electronegativity for this task. Here’s the bottom line lesson for the resonance structures we’ll evaluate today.
Hopefully this makes some sense! Charged resonance forms are less stable than neutral resonance forms. So if we absolutely must form a charged resonance form, it makes sense to put the negative charge on the atom best able to stabilize it. How do we know which atoms stabilize negative charge the best? Well, a pKa table will give you a really good idea. But beyond that, if you look at the five key factors that influence acidity, one of the most important factors is the electronegativity of an atom. After all, electronegativity is ultimately a measure of to what extent an atom is able to stabilize negative charge.
2. What Are The Best Resonance Structures Of Acetone (Propanone)?
So hopefully it should come as no surprise as we walk through these three examples that the second-best resonance forms are the ones where negative charge ends up on the more electronegative atom.
Let’s start by looking at a simple carbonyl compound, acetone (propanone).
If we look at the possible curved-arrow “moves” for drawing the resonance forms of this molecule, there’s two possibilities.
In the first possibility, we draw an arrow from the π bond to the oxygen atom, putting a negative charge on the oxygen and leaving behind a positive charge on the carbon.
In the second, we’re making the carbon negative and leaving behind a positive charge on the oxygen. Not only is there a positive charge on the oxygen, it has less than a full octet. This is an extremely unstable situation.
So hopefully it’s clear that:
- the best resonance form is the neutral form with full octets
- the second-best resonance form is the one with a negative charge on oxygen (and less than a full octet on carbon), and
- the resonance form where there is a negative charge on carbon and less than a full octet on oxygen is insignificant.
Experiment bears this out. Calculations of the charge density on acetone reveal that the carbon is electropositive and the oxygen is electronegative, as per what we’d expect from electronegativity differences. So the molecule can be thought of as a hybrid of the best and second-best resonance forms.
3. What Are The Best Resonance Structures Of This Imine?
Likewise, the resonance forms for the imine below similar behavior.
As expected, calculations of electron density for this imine show that there is considerable positive charge density on the carbon and a high density of negative charge on the nitrogen. As you’d expect, the resonance form where there’s negative charge on carbon gets very little weight.
4. What Are The Best Resonance Structures Of The Acetate Ion?
Finally we come to the acetate ion, which we discussed previously. Again, the second-best resonance form is that where there’s a positive charge on the carbon (and the worst is the one where it bears a negative charge).
5. Apply The Rule Of Electronegativity To Determine The “Second-Best” Resonance Structures For These Molecules
With these examples in mind, can you apply the rule to determine the “second-best” resonance forms for each of these molecules?
To see the answer, hover here or click on this link.
Next time I’ll go into a few more details on evaluating resonance forms based on lessons we learn from acidity and basicity.
Next Post: Evaluating Resonance Forms (3) – Where to Put Negative Charges
15 thoughts on “How To Find The Best Resonance Structure By Applying Electronegativity”
very useful website.helped me during jee prep
I have found in various books that having three charges in a resonance structure would make it insignificant.Is this gospel for resonance structures? When I practice doing RS I always treat RS with three charges as insignificant. If this is the case why is the acetate ion with three charges not insignificant?
Also, when I do this structure I just make two pushing arrows at the same time to get the other major RS. So what is the point to doing the one with three charges?
thank you! I have one more question I am having a hard time with! In the problem set we are supposed to draw the second best resonance structure but for some of the problems it looks like the second best answer in the key is a better choice then the original molecule? For example on the 6th molecule with the positive charge on the oxygen, the answer key gave a resonance structure with the positive charge on the carbon as the better choice even though negative charges should be on the more negative atom?
why can there be 10 valence electrons on phosphorus in the 4th problem in the question set?
Third row elements such as phosphorus and sulfur can have more than 8 electrons in their valence shell.
In the last five, except the 2nd last, wouldn’t the resonating forms given in the answers be the best forms? As you explained, more electronegative elements having a +ve charge and less than octet valence shell configuration are very unstable. So wouldnt those resonating forms, where the +ve charge is on the less electronegative element and where the more electronegative one is neutral with octet, be more stable? A reply would be appreciated.
Yes, they are the best. The question asked for the “second best” forms!
Why can sulphur have less than a full octet?
It doesn’t. In the resonance form of dimethyl sulfoxide written (CH3)2-S(+)–O(-) there is actually a lone pair on the sulfur.
in the case of CO2 there can be a resonating structure with carbon triple bonded and single bonded with oxygen [with + and – charges on oxygen] and this should be the second best structure because here more no of covalent bond is present which increases the stability.
Please tell me where am I wrong… After reading the next article in this series, this came to my mind :
In the 2nd problem of the second best resonating forms (S=O), shouldn’t the negative charge be on S (least basic) ?
In fact there’s even an example in the next article in the “Factor-2” section, which shows that -ve charge would be more stable on S atom.
Good point. If the negative charge was on S however, the oxygen would have less than a full octet, which is very unstable. I should have mentioned in the section on positive charge that sulfur can have less than a full octet.
Love this website, help me a lot for the DAT exam! Introduced it to lots of friends.
Can I get the answer to second best resonating forms? Willing to match my answers
Yep – just put them up. Thanks for commenting!