Metal-π Interactions Between M(CO)₃ and Halobenzene. Cooperative Effects on Halogen Bonding

Area of Science:

• Organometallic Chemistry
• Computational Chemistry
• Supramolecular Chemistry

Background:

• Metal-arene interactions are crucial in catalysis and materials science.
• Understanding bonding nuances informs the design of novel organometallic complexes.

Purpose of the Study:

• To investigate the bonding characteristics between M(CO)3 metal complexes and benzene/halobenzene systems.
• To explore the influence of metal identity and ring substitution on M···π interactions.

Main Methods:

• Density Functional Theory (DFT) calculations were employed.
• Systematic examination of metals from the 3d and 4d periods (Groups 6-12).

Main Results:

• Bonding strength and geometry vary significantly with metal position.
• Left-side metals form strong, potentially coordinate covalent bonds, inducing ring distortions.
• Right-side metals exhibit weaker, noncovalent interactions.
• Halogenation causes minimal changes to M···π bonding but enhances halogen bond strength via charge transfer.

Conclusions:

• Metal identity dictates the nature and strength of M···π bonds.
• Cooperative effects between M···π and halogen bonding are observed but are modest.
• Findings provide insights into tuning metal-arene interactions and related phenomena.