The Structure-correlation Principle
The structure-correlation principle states that that structural changes which occur along the reaction coordinate can reveal themselves in the ground state as deviations of bond distances and angles from normal values along the reaction coordinate. According to this theory if one particular bond length on reaching the transition state increases then this bond is already longer in its ground state compared to a compound not sharing this transition state. One demonstration of this principle is found in the two bicyclic compounds depicted below. The one on the left is a bicylcooctene which at 200°C extrudes ethylene in a retro-Diels–Alder reaction.
Compared to the compound on the right (which, lacking an alkene group, is unable to give this reaction) the bridgehead carbon-carbon bond length is expected to be shorter if the theory holds because on approaching the transition state this bond gains double bond character. For these two compounds the prediction holds up based on X-ray crystallography.
Read more about this topic: Transition State
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