Metathesis Reactions between Heavy d-8 Fluorides and I(III)-Pyridine Complexes

Area of Science:

• Inorganic Chemistry
• Organometallic Chemistry
• Fluorine Chemistry

Background:

• Cationic gold(III) complexes are typically considered electrophilic.
• The reactivity of gold-fluorine bonds in cationic complexes is not well understood.
• Understanding the nucleophilicity of gold-fluorine fragments is crucial for designing new gold-based reagents.

Purpose of the Study:

• To investigate the reaction between a cationic gold(III) fluoride complex and an iodine(III) species.
• To elucidate the reaction mechanism and determine the role of the Au-F bond.
• To assess the nucleophilic potential of the Au(III)-F fragment.

Main Methods:

• Synthesis and characterization of trans-[AuF2(pyridine)2]+.
• Reaction of trans-[AuF2(pyridine)2]+ with [PhI(pyridine)2]2+.
• Mechanistic studies using model palladium and platinum analogues.
• Spectroscopic analysis to identify reaction products.

Main Results:

• The reaction yielded PhIF2 and [Au(pyridine)4]3+.
• Mechanistic investigations suggested nucleophilic attack by the Au-F bond onto the iodine(III) center.
• A redox process was ruled out as the primary reaction pathway.
• The Au(III)-F fragment demonstrated nucleophilic character despite the electron-poor nature of the complex.

Conclusions:

• Gold(III) fluoride complexes can exhibit nucleophilic behavior.
• The Au(III)-F fragment acts as a nucleophile in reactions with iodine(III) compounds.
• This finding expands the known reactivity patterns of cationic gold complexes.