In an earlier post, I re-visited the conformational analysis of cyclohexane by looking at the vibrations of the entirely planar form (of D6h symmetry). The method also gave interesting results for the larger cyclo-octane ring. How about a larger leap into the unknown?
Let us proceed as follows. One fun game to play in chemistry is to invoke iso-electronic substitutions. In this case, we can subtitute a nitrogen and a boron atom for a pair of carbons. Thrice invoked, it leads to a molecule known as cyclotriborazane.
This species is in fact very well known, and a crystal-structure was determined some time ago (DOI: 10.1021/ja00786a022). It is worth considering some of its properties.
The crystal structure however shows clearly that the chair is still the favoured conformation. Equally intriguing, one might expect the three blue hydrogens to stack up to attract electrostatically to the three red hydrogens. But you can see from the crystal packing if you activate the model below that this does not happen!
What of the vibrational analysis, conducted as it was for cyclohexane itself (DOI: 10042/to-4170). Well, just as before, for the planar geometry, three imaginary modes are calculated (A2“, E”) and just as before, they distort the geometry in the direction of a chair (Cs symmetry), a C2-disymmetric twist boat (with a predicted optical rotation of -54°) and a boat respectively (the latter, as before, being a transition state connecting the two C2-enantiomers). But here we get a surprise! According to the B3LYP/6-311G(d,p) model, the final resting energy for the chair is almost the same (indeed 0.2 kcal/mol higher in free energy) as the twist-boat. Perhaps that blue/red repulsion did have an effect after all! If you look at the calculated structure, you can indeed see that the blue/red hydrogens are splayed-out, avoiding each other! This is one of those molecules where one might have expected surprises. In the end, it is surprising at how similar cyclotriborazane is to its iso-electronic cousin cyclohexane.In an earlier post, I discussed a phenomenon known as the "anomeric effect" exhibited by…
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