Site-selective nitrenoid insertions utilizing postfunctionalized bifunctional rhodium(ii) catalysts

Area of Science:

• Organometallic Chemistry
• Catalysis
• Materials Science

Background:

• Dirhodium(ii) tetracarboxylate complexes are valuable in catalysis.
• Existing methods limit postfunctionalization of these complexes.
• Tailoring dirhodium complexes for specific applications remains a challenge.

Purpose of the Study:

• To develop a novel strategy for preparing functionalizable dirhodium(ii) complexes.
• To explore the postfunctionalization of dirhodium tetracarboxylate complexes with a free amino group.
• To investigate the catalytic applications of these modified complexes, including site-selective reactions.

Main Methods:

• Synthesis of dirhodium(ii) tetracarboxylate complexes with a free amino group.
• Postfunctionalization of the amino group with various organic moieties (alkynes, alkenes, nucleophiles).
• Demonstration of site-selective nitrenoid insertions using a urea-containing dirhodium(ii) complex controlled by hydrogen bonding.

Main Results:

• Successful preparation of Rh2(A)4 complexes with accessible amino groups.
• Versatile incorporation of diverse functional groups via postfunctionalization.
• Creation of new polymeric, bifunctional, and polymetallic catalysts.
• Achieved site-selective nitrenoid insertions through remote hydrogen bonding control.

Conclusions:

• The reported strategy provides a versatile platform for dirhodium(ii) complex functionalization.
• This approach enables the development of advanced catalytic systems and materials.
• Hydrogen bonding offers a powerful tool for controlling reactivity in dirhodium-catalyzed reactions.