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Loren McCune

Is there really any difference between Resonance and Mesomeric effect?

Demi Blye  Follow

Have you read the poem "Five Blind Men and the Elephant", where each person tries to explore an elephant and comes with their own version. Someone touches elephant's trunk and calls it a snake, someone touches the legs and calls it a tree trunk and so on. The world of molecules and sub-atomic world is indeed that elephant, and chemists are unfortunately unable to see them- to see what is happening. Hence each one comes up with an intelligent story only to be improved or discarded later. So the lesson is that don't take everything literally (incuding the statements made by high school or college teachers). Moreover, do not rely on the web-answers including this one ultimate facts.

In the same way the concept of resonance was developed really a long time ago. Keep in mind that none of the structure you draw with resonance reflects a reality. It is a subtle and an esoteric way of human expression that we do not know how it looks like in reality. X-rays allow you see the arrangement of solids in space but it does not let you see electrons, there is no physical arrow pushing going on and there no electron dance going on. It is all human imagination.

Think of the classic benzene example, (image from Wikipedia). None of the structures reflect a reality, hence the term resonance hybrid, because benzene does not chemically behave as if its double bonds were "static". The C-C bond distances in the ring have to be different, otherwise.

enter image description here

There is a very nice article by Robert C. Kerber titled If It’s Resonance, What Is Resonating? in the Journal of Chemical Education (It is freely available on Google Scholar). Have you wondered why the name "Resonance"?

History The use of multiple structures to represent compounds with(what we now call) delocalized bonding (4) was pioneered in Germany byArndt (5) and in Britain by Ingold (6). Their ideas were basedessentially on chemical intuition. In the United States, Pauling$(7,8)$ in his pioneering applications of the principles of quantummechanics to chemistry, came to a similar description from a differentstarting point. Whereas the concepts of describing a single substancein terms of multiple structures may not have differed significantly,the terminology did. Arndt coined the term $Zwischenstufe$ for thehybrid structure, while Ingold opted for the equivalent term (derivedfrom Greek) mesomer. He proposed for the concept the terms mesomericeffect or mesomerism. The cognate term mesomerie came into use inFrench and German. Pauling preferred the term resonance, derived fromvalence bond theory (see below). Pauling and Ingold were well aware ofeach other's terminology, and each offered reasons for rejecting thealternative proposal: Because the resonating system does not have astructure intermediate between those involved in the resonance, butinstead a structure which is further changed by the resonancestabilization, I prefer not to use the word 'mesomerism,' suggested byIngold, for the resonance phenomenon.

  • L. Pauling (9) Pauling describes the phenomenon under the name 'resonance,' which, as is well known, is based on the mathematicalanalogy between mechanical resonance and the behavior of wavefunctions in quantum mechanical exchange phenomena. There appears,however, to be some possibility that this method of description maysuggest an analogy which has never been intended.
  • C. K. Ingold (6) Pauling's argument conflates the concepts of structure and energy. Moreover, his chosen term resonance is derivedfrom an analogy to coupled oscillators, which also lacks energeticimplications: "There is no close classical analogue of resonanceenergy" (10). So neither term includes explicit reference to energyconsiderations, weakening Pauling's argument. For use in discussingthe structure (i.e., geometry) of the hybrid, Ingold's argument seemsthe more persuasive. His recognition of the gratuitous oscillatoryaspect of the analogy is prophetic of the subsequent experience ofgenerations of students.*

Your next query on mesomerism and IUPAC. In terms of terminology, most chemists follow the IUPAC recommendation's on terminologies. You can call mesomerism as a type of resonance. See this reference "Introductory Organic Chemistry and Hydrocarbons: A Physical Chemistry Approach" by Caio Lima Firme on pg 111-112.

As Ingold himself defined: "Mesomerism is an extension of valencytheory (that is the classical valence bond theory) and, like allvalency theory, is founded in the quantum theory (...). Thefundamental wave-property in the theory of valency is resonance $-$the resonance of connected standing waves; their mutual perturbationreplaces these waves by new standing waves" (Ingold 1938). Ingoldexemplified the resonance theory by using the two resonancestructures: $\mathrm{R}_{2} \mathrm{~N}-\mathrm{CH}=\mathrm{N}^{+}> \mathrm{R}_{3}$ and $\mathrm{R}_{3}^{+}> \mathrm{N}=\mathrm{C}(\mathrm{H})-\mathrm{NR}_{2}$ with their ownstanding waves which resonate to form the real molecule. Ingold statedthat the term mesomerism was given to account for the specialimportance of resonance in organic chemistry. He also said: "Whenmesomerism was first recognized as a general phenomenon in organicchemistry, it was appreciated as an electron displacement than as anenergy disappearance" (Ingold 1938). From this point on, we can saythat mesomerim is equivalent to resonance type 3 (resonance involvingonly charged and/or neutral covalent structures), although IUPACrecognizes mesomerism as essentially synonymous with resonance (whichcould include all types of resonance). Nonetheless, IUPAC adds thatmesomerism is "particularly associated with the picture of$\pi$-electrons as less localized in an actual molecule than in aLewis formula” (IUPAC Gold Book). Then, mesomeric state is the same asresonance hybrid and energy of mesomerism is synonymous to resonanceenergy (Ingold 1938).

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Edwin Amhanokhai A.  Follow
Again, just recall the blind men and the elephant (molecule)! Both were highly respected chemists.More
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J.W  Follow
Yes, I understandMore
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Huang Lu  Follow
Thank you, seems like its all the result of conflict between Ingold and Pauling.More
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