Synthesis, Structure, and Bonding of a Xe^IV Transition-Metal Coordination Complex, F₃ XeF_b - - -WOF₄

Area of Science:

• Inorganic Chemistry
• Coordination Chemistry
• Fluorine Chemistry

Background:

• Xenon tetrafluoride (XeF₄) is a strong oxidative fluorinating agent.
• Tungsten oxyfluoride (WOF₄) acts as a moderate fluoride-ion acceptor.
• The synthesis of novel xenon coordination complexes is of significant interest.

Purpose of the Study:

• To synthesize and characterize a new coordination complex involving Xe^IV and a transition metal.
• To investigate the bonding interactions and structural features of the F₃XeF_b-WOF₄ complex.
• To explore the stability and synthetic feasibility of related complexes.

Main Methods:

• Synthesis of F₃XeF_b-WOF₄ in CFCl₃ solvent.
• Single-crystal X-ray diffraction for structural determination.
• Raman spectroscopy for vibrational analysis.
• Computational calculations to understand bonding and stability.

Main Results:

• The coordination complex F₃XeF_b-WOF₄ was successfully synthesized and characterized.
• The complex features XeF₄ coordinating to WOF₄ via a W-F_b bond, trans to the W=O group.
• Spectroscopic data indicate the XeF₃ moiety gains positive character upon coordination.
• Computational analysis reveals the W-F_b bond is primarily electrostatic with a significant σ-hole contribution, explaining the bent bond angle.
• Calculated stabilities suggest related Mo and Cr complexes are less favorable.

Conclusions:

• F₃XeF_b-WOF₄ is the first characterized transition-metal coordination complex of Xe^IV.
• The bonding in this complex is a unique interplay of electrostatic and orbital interactions.
• The findings provide a foundation for understanding Xe^IV coordination chemistry and guide future synthetic efforts.