Sigma-hole bonding: molecules containing group VI atoms

Area of Science:

• * Inorganic Chemistry
• * Computational Chemistry
• * Chemical Physics

Background:

• * Divalently-bonded Group VI atoms exhibit unusual noncovalent interactions with nucleophiles.
• * These interactions are highly directional and have been observed experimentally and computationally.

Purpose of the Study:

• * To explain the nature of noncovalent interactions involving Group VI atoms.
• * To introduce and define the

Main Methods:

• * Computational analysis of electrostatic potential on atomic surfaces.
• * Investigation of electron density distribution and orbital characteristics.

Main Results:

• * Identification of positively charged regions on the outer surfaces of Group VI atoms along covalent bond extensions.
• * Attribution of these positive regions to a

Conclusions:

• * The sigma-hole concept provides a clear explanation for the observed noncovalent interactions.
• * Interaction strength is influenced by atomic electronegativity, polarizability, and the electron-withdrawing nature of bonded groups.