A base-free thorium-terminal-imido metallocene: synthesis, structure, and reactivity

Area of Science:

• Organometallic Chemistry
• Thorium Chemistry
• Catalysis

Background:

• Thorium metallocenes are versatile precursors in organometallic synthesis.
• Understanding the reactivity of thorium-imido complexes is crucial for developing new catalytic applications.

Purpose of the Study:

• To synthesize and characterize base-free thorium terminal-imido metallocenes.
• To investigate the reactivity of these novel thorium complexes with various reagents.
• To explore their potential as catalysts in organic transformations.

Main Methods:

• Synthesis of thorium diamides from thorium metallocenes and primary amines.
• Thermal conversion of diamides to thorium imido metallocenes.
• Reactivity studies with electrophiles, unsaturated reagents, and sulfur.
• Density Functional Theory (DFT) calculations to elucidate reaction mechanisms.

Main Results:

• Successful synthesis of base-free thorium terminal-imido metallocenes.
• Demonstrated reactivity of imido metallocene 10 with sulfur to form a metallacycle.
• Imido metallocene 10 identified as an intermediate in catalytic hydroamination and a catalyst for nitrile trimerization.
• DFT studies provided insights into observed reactivity patterns.

Conclusions:

• Base-free thorium imido metallocenes are stable and synthetically accessible.
• These complexes exhibit unique reactivity, enabling new chemical transformations.
• Thorium imido metallocenes hold promise as efficient catalysts in organometallic chemistry.