Trithio-chloro molybdate [MoClS3]-: a versatile precursor for molybdenum trisulfido complexes.

Area of Science:

• Inorganic Chemistry
• Organometallic Chemistry
• Bioinorganic Chemistry

Background:

• Molybdenum-sulfur complexes are crucial in bioinorganic chemistry, particularly in enzymes like nitrogenase.
• Understanding the synthesis and reactivity of molybdenum-sulfur clusters is key to mimicking enzyme active sites.

Purpose of the Study:

• To develop a convenient synthetic route to mononuclear molybdenum trisulfido complexes.
• To explore the reactivity of trithiomolybdate with silylating agents.
• To synthesize and characterize novel molybdenum trisulfido derivatives, including potential biomimetic models.

Main Methods:

• Reaction of tetraphenylphosphonium trithiomolybdate with trimethylchlorosilane.
• Subsequent reactions of the intermediate trithio-chloro molybdate with various potassium salts.
• X-ray crystallography for structural determination of key complexes.

Main Results:

• High-yield synthesis of trithio-chloro molybdate [PPh 4][MoClS 3] via a siloxy intermediate.
• Generation of a diverse series of mononuclear molybdenum trisulfido complexes with varying ligands (sulfur, nitrogen, oxygen-based).
• Synthesis of a citrate complex that models the molybdenum site of the nitrogenase FeMo-cofactor.
• Structural elucidation of several synthesized complexes using X-ray crystallography.

Conclusions:

• A facile synthetic pathway to mononuclear molybdenum trisulfido complexes has been established.
• The synthesized complexes offer a versatile platform for studying molybdenum-sulfur chemistry.
• The citrate complex represents a significant step towards understanding the nitrogenase active site.