Aurophilic interactions in a mixed-valent Au^I/III 4-cyanothiazole complex

Area of Science:

• Inorganic Chemistry
• Materials Science
• Computational Chemistry

Background:

• Gold(I)...gold(I) contacts are common in gold compounds.
• Mixed-valent gold(I)/gold(III) complexes with direct gold-gold interactions are exceptionally rare in unsupported systems.

Purpose of the Study:

• To report the synthesis and structural characterization of a novel mixed-valent gold complex.
• To analyze the nature of the Au(I)...Au(III) interaction using computational methods.

Main Methods:

• Synthesis of bis(4-cyanothiazole)gold(I) tetrachloridoaurate(III).
• Single-crystal X-ray diffraction for structural analysis.
• Density Functional Theory (DFT)-based quantum mechanical calculations.
• Quantum Theory of Atoms in Molecules (QTAIM) analysis.

Main Results:

• The new complex exhibits one of the shortest reported Au(I)...Au(III) contacts (3.294(4) Å) in unsupported mixed-valent systems.
• DFT-QTAIM calculations provide insights into the electronic structure and bonding characteristics of the Au(I)...Au(III) interaction.

Conclusions:

• The study presents a rare example of a mixed-valent gold complex with a significant Au(I)...Au(III) contact.
• Computational analysis confirms the nature of this interaction, contributing to the understanding of bonding in gold compounds.