Rhodafuran from a methoxy(alkenyl)carbene by the rhoda-1,3,5-hexatriene route

Area of Science:

• Organometallic Chemistry
• Rhodium and Iridium Catalysis
• Synthetic Organic Chemistry

Background:

• Organometallic complexes are crucial in catalysis and materials science.
• Understanding the influence of metal centers (like Rhodium and Iridium) on reactivity is key to designing new synthetic pathways.
• Carbene complexes offer unique reactivity for forming cyclic structures.

Purpose of the Study:

• To synthesize a novel methoxy(alkenyl)carbenerhodium complex as a starting material.
• To investigate the effect of the metal center (Rhodium vs. Iridium) on the formation of rhodacycle complexes.
• To develop an efficient method for synthesizing metallafuran complexes.

Main Methods:

• Synthesis of a specific methoxy(alkenyl)carbenerhodium complex: [RhCp*Cl{[double bond, length as m-dash]C(OMe)CH[double bond, length as m-dash]CPh2}(PMe3)]PF6 (2).
• Exploration of C-H bond activation of a phenyl ring to form indenylrhodium complexes (η3 and η5).
• Insertion of terminal alkynes into the rhodium-carbene bond.

Main Results:

• Successful synthesis of the target methoxy(alkenyl)carbenerhodium complex.
• Achieved η3 and η5 indenylrhodium complexes via C-H activation.
• Reported the first synthesis of rhodafuran complexes using terminal alkynes and rhoda-1,3,5-hexatriene intermediates.

Conclusions:

• The study demonstrates an efficient new route to metallafuran complexes.
• The developed method provides a valuable tool for organometallic synthesis.
• Highlights the distinct reactivity of rhodium in carbene complex transformations.