Small Gold(I) and Gold(I)-Silver(I) Clusters by C-Si Auration

Area of Science:

• Organometallic Chemistry
• Materials Science
• Catalysis

Background:

• Auration of phosphines is a key route to novel metal clusters.
• Ortho-metalation offers unique bonding and structural motifs.
• Understanding cluster formation is crucial for developing new catalysts.

Purpose of the Study:

• To synthesize and characterize novel gold and gold-silver clusters.
• To investigate the role of ortho-metalated phosphines in cluster formation.
• To evaluate the catalytic activity of the synthesized clusters.

Main Methods:

• Reaction of (L-TMS)AuCl with silver salts (AgX) and silver oxide (Ag2O).
• Synthesis of hexagold clusters [Au6L4](X)2.
• Formation of gold-silver clusters [Au4Ag2L4](X)2 and other cluster types.
• Characterization of intermediates like oxo-trigold(I) species [Au3O]+.

Main Results:

• Formation of gold clusters [Au6L4](X)2 and gold-silver clusters [Au4Ag2L4](X)2.
• Identification of ortho-metalated phosphines with 3c-2e Au-C-M bonds (M=Au/Ag).
• Observation of catalytic activity in alkyne activation by clusters with PAu-Au-AuP motif.

Conclusions:

• Ortho-trimethylsilyl arylphosphines are effective precursors for gold and gold-silver clusters.
• The synthesized clusters exhibit unique structural features and catalytic properties.
• These findings open avenues for designing new homogeneous catalysts.