Nonheme binuclear transition metal complexes with hydrosulfide and polychalcogenides

Area of Science:

• Inorganic Chemistry
• Organometallic Chemistry
• Coordination Chemistry

Background:

• Chalcogen-containing ligands, such as hydrosulfide (HS-) and polychalcogenides (E2-, E = S, Se), are crucial in forming diverse transition metal complexes.
• While organometallic complexes with these ligands are common, non-organometallic analogues featuring N-/O-donor ligands are less explored.
• Existing synthetic methods for hydrosulfido and polychalcogenido complexes often require harsh conditions or lead to undesired oligomers.

Purpose of the Study:

• To develop new, efficient synthetic methodologies for binuclear transition metal complexes incorporating hydrosulfide (HS-) or polychalcogenide (S2-, Se2-) ligands.
• To explore the synthesis of non-organometallic complexes with N-/O-donor ligands using these novel methods.
• To investigate the structural properties and reactivity of the newly synthesized complexes.

Main Methods:

• Developed a novel room temperature (RT) method involving transition metal-mediated hydrolysis of thiolates for synthesizing transition metal-hydrosulfido complexes.
• Established a new RT redox reaction of coordinated thiolates with exogenous elemental chalcogens for preparing transition metal-polychalcogenido complexes.
• Characterized the resulting binuclear complexes to understand their structural and chemical properties.

Main Results:

• Successfully synthesized two new classes of binuclear transition metal complexes featuring hydrosulfide (HS-) or polychalcogenide (S2-, Se2-) ligands.
• Demonstrated the efficacy of the new synthetic methods, enabling complex formation at room temperature.
• The developed methods provide access to non-organometallic complexes, expanding the known chemistry of these ligand types.

Conclusions:

• The newly developed synthetic routes offer mild and efficient access to previously challenging transition metal complexes.
• These methods facilitate the preparation of binuclear complexes with hydrosulfide and polychalcogenide ligands under ambient conditions.
• The study expands the scope of non-organometallic coordination chemistry involving chalcogen-based ligands.