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Pnictogen Interactions with Nitrogen Acceptors
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DOI：10.1002/anie.202304960.png)
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Abstract
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Stabilizing nitrogen pnictogen bond interactions were measured using molecular rotors. Intramolecular C=O center dot center dot center dot N interactions were formed in the bond rotation transition states which lowered the rotational barriers and increased the rates of rotation, as measured by EXSY NMR. The pnictogen interaction energies show a very strong correlation with the positive electrostatic potential on nitrogen, which was consistent with a strong electrostatic component. In contrast, the NBO perturbation and pyramidalization analyses show no correlation, suggesting that the orbital-orbital component is minor. The strongest C=O center dot center dot center dot N pnictogen interactions were comparable to C=O center dot center dot center dot C=O interactions and were stronger than C=O center dot center dot center dot Ph interactions, when measured using the same N-phenylimide rotor system. The ability of the nitrogen pnictogen interactions to stabilize transition states and enhance kinetic processes demonstrates their potential in catalysis and reaction design.
Keywords:
Molecular Rotors
Nitro-Groups
Non-Covalent Interaction
Supramolecular Chemistry
pi-Hole
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