Dinuclear copper(I) and copper(I)/silver(I) complexes with condensed dithiolato ligands

Area of Science:

• Inorganic Chemistry
• Coordination Chemistry
• Organometallic Chemistry

Background:

• Copper complexes with sulfur-containing ligands are crucial in various catalytic processes.
• Understanding the reactivity and structural diversity of polynuclear metal complexes is essential for developing new materials and catalysts.
• The role of metallophilic interactions in stabilizing complex structures and influencing reactivity is an active area of research.

Purpose of the Study:

• To synthesize and characterize novel dinuclear copper and heterodinuclear silver-copper complexes.
• To investigate the solution behavior, including thioketene-exchange equilibria, of these complexes.
• To explore the structural features, particularly metallophilic interactions, using X-ray diffraction.

Main Methods:

• Synthesis of copper and silver-copper complexes via reactions of a Cu(III) precursor with copper(I) salts and silver(I) perchlorate in the presence of phosphine ligands.
• Characterization of synthesized complexes using spectroscopic techniques and single-crystal X-ray diffraction.
• Investigation of solution equilibria through NMR spectroscopy and analysis of reaction products.

Main Results:

• Successful synthesis of dinuclear copper complexes ([Cu2{[SC=(t-Bu-fy)]2S}(PR3)n]) and heterodinuclear silver-copper complexes ([AgCu{[SC=(t-Bu-fy)]2S}(PR3)3]).
• Observation of thioketene-exchange equilibria in solution for copper complexes, leading to the formation of tetranuclear species and complexes with altered ligand stoichiometry.
• X-ray crystal structures reveal short Ag...Cu metallophilic contacts in heterodinuclear complexes, indicating significant metal-metal bonding.

Conclusions:

• The studied copper and silver-copper complexes display rich solution chemistry, including ligand exchange and complex aggregation/disaggregation processes.
• The presence of Ag...Cu metallophilic contacts in the solid state suggests potential for unique electronic and catalytic properties.
• This work expands the library of polynuclear sulfur-ligated metal complexes and provides insights into their structural and reactivity patterns.