Catalytic Sulfur-Atom Transfer Enabled by a Bis(disulfide) Titanium Complex

Area of Science:

• Organometallic Chemistry
• Catalysis
• Sulfur Chemistry

Background:

• Multi-electron processes are crucial for small molecule activation but underdeveloped for titanium.
• Low-valent titanium precursors are difficult to access, limiting its use in multi-electron transformations.

Purpose of the Study:

• To report a novel four-electron transformation involving a titanium(IV) complex.
• To synthesize a rare titanium bis(disulfide) complex.
• To utilize this complex for catalytic atom-transfer reactions.

Main Methods:

• Synthesis of a novel titanium bis(disulfide) complex via a four-electron transformation.
• Catalytic application of the complex for isothiocyanate synthesis from isonitriles.
• Mechanistic investigations including reaction kinetics and quantum chemical calculations.

Main Results:

• Successfully synthesized a rare titanium bis(disulfide) complex in a spiropentane motif.
• Demonstrated efficient and selective catalytic synthesis of isothiocyanates at ambient temperatures.
• The catalytic reaction tolerates oxygen-containing functional groups, outperforming noble-metal catalysts.

Conclusions:

• The study presents a new four-electron transformation for titanium, yielding a unique sulfur-rich complex.
• The developed catalytic system offers an efficient and versatile method for isothiocyanate synthesis.
• This work advances multi-electron processes and atom-transfer catalysis using group IV metals.