Wolfium Bonds with π Systems as Electron Donors.

Area of Science:

• Inorganic Chemistry
• Theoretical Chemistry
• Computational Chemistry

Background:

• Attractive interactions between group 6 elements and electron-rich moieties are termed "wolfium bonds."
• Understanding these interactions is crucial for predicting chemical reactivity and designing novel materials.

Purpose of the Study:

• To theoretically investigate the nature and strength of wolfium bonds.
• To analyze the factors influencing the stability of these interactions involving group 6 elements (Cr, Mo, W) and various π systems.

Main Methods:

• Density Functional Theory (DFT) calculations were performed at the ωB97XD/aug-cc-pVTZ level.
• Interaction energies, charge transfer, and orbital interactions were analyzed for WnF4O/WnF2O compounds with C2H2, C2H4, and C6H6.

Main Results:

• Wolfium bond formation resulted in interaction energies ranging from -3.74 to -10.86 kcal/mol.
• Electrostatic contributions were found to be the dominant force in these interactions.
• WnF4O systems were generally more stable than WnF2O counterparts, except for the CrFxO system.

Conclusions:

• The study confirms the presence of weak yet significant wolfium bonds between group 6 elements and electron-rich π systems.
• Charge transfer analysis indicated magnitudes between 0.0114 and 0.0946e.
• The primary orbital interaction identified was πC-C→BD*Wn-O.