A Thorium Chalcogenolate Series Generated by Atom Insertion into Thorium-Carbon Bonds

Area of Science:

• Organometallic Chemistry
• Thorium Chemistry
• Chalcogen Insertion Reactions

Background:

• Thorium complexes are of interest for their unique reactivity.
• Understanding atom insertion reactions is crucial for synthetic chemistry.

Purpose of the Study:

• To synthesize and characterize new thorium chalcogenolate complexes.
• To investigate the insertion of chalcogen atoms into thorium monoalkyl complexes.
• To explore the reactivity of thorium complexes with oxygen atom transfer reagents.

Main Methods:

• Synthesis of thorium monoalkyl complex Th(CH2SiMe3)(L3).
• Reaction with various chalcogen sources (S, SS, Se, Te) to form chalcogenolate complexes.
• Characterization using NMR spectroscopy, FTIR, elemental analysis, and X-ray crystallography.
• Investigation of reactions with trimethylamine N-oxide (Me3NO).

Main Results:

• A series of thorium chalcogenolate complexes (Th(ECH2SiMe3)(L3), E = S, SS, Se, Te) were successfully synthesized.
• The first alkyl disulfide thorium species was prepared, demonstrating controllable atom insertion.
• Reaction with Me3NO resulted in C-H activation and alkoxide formation, not oxygen insertion.

Conclusions:

• Thorium monoalkyl complexes can undergo controlled chalcogen atom insertion.
• The reactivity of thorium complexes can be tuned by the choice of transfer reagent.
• This work expands the known chemistry of thorium organometallics.