Are Heavy Pnictogen-π Interactions Really "π Interactions"?

Area of Science:

• Chemical Physics
• Computational Chemistry
• Supramolecular Chemistry

Background:

• Noncovalent interactions involving heavy pnictogens (As, Sb, Bi) and π-arenes are crucial in crystal engineering and catalysis.
• The strength of these interactions is traditionally attributed to dispersion and donor/acceptor forces, primarily linked to π-arene presence.

Purpose of the Study:

• To computationally investigate the interactions between heavy pnictogens and cyclohexane.
• To compare these interactions with those involving benzene to reassess current understanding.
• To analyze the energetic components and their interplay in these systems.

Main Methods:

• Utilized state-of-the-art computational methods for thorough energetic analysis.
• Compared interaction models of heavy pnictogens with cyclohexane versus benzene.

Main Results:

• The study challenges the established concept that π-arenes are essential for strong heavy pnictogen interactions.
• Energetic component analysis revealed intricate interplay influencing overall system stability.
• Pnictogen compounds significantly impacted cyclohexane's conformational equilibrium, altering the stability of chair and boat-twist conformers.

Conclusions:

• The role of π-arenes in heavy pnictogen interactions may need revision.
• Heavy pnictogen-cyclohexane interactions offer insights into noncovalent bonding.
• Potential application in using tunable dispersion energy donors to stabilize specific molecular conformations.