Cationic Noncovalent Interactions: Energetics and Periodic Trends

Area of Science:

• Physical Chemistry
• Computational Chemistry
• Chemical Thermodynamics

Background:

• Noncovalent interactions are fundamental to molecular recognition and self-assembly.
• Understanding these interactions is crucial for fields ranging from supramolecular chemistry to drug design.
• Existing data on metal cation-neutral molecule interactions are scattered and require systematic compilation.

Purpose of the Study:

• To provide a comprehensive review of thermodynamic data for noncovalent interactions involving metal cations and neutral molecules.
• To compile and evaluate existing thermochemical data, reanchoring it to 0 K bond dissociation energies where possible.
• To identify and discuss trends in these interactions and relate them to molecular properties.

Main Methods:

• Literature survey and critical evaluation of thermochemical data.
• Compilation of data into extensive tables for various ligand types.
• Re-evaluation and adjustment of literature thermochemistry to 0 K bond dissociation energies.

Main Results:

• Extensive tables of thermodynamic data for metal cation interactions with small molecules, organic ligands, π-ligands, inorganic ligands, and biological systems.
• Inclusion of hydration data for metalated biological systems and selected proton-based systems.
• Analysis of trends in bond dissociation energies and their correlation with molecular structure and properties.

Conclusions:

• The compiled data provides a valuable resource for researchers studying noncovalent interactions.
• Trends identified offer insights into the nature of metal-ligand bonding.
• This work facilitates a deeper understanding of cation-π, cation-ligand, and hydration interactions.