Persistent acyclic Cp*Ir(III) complexes and their reactivities in cross-coupling reactions

Area of Science:

• Organometallic Chemistry
• Iridium Catalysis
• Synthetic Chemistry

Background:

• Iridium(III) complexes are crucial in organometallic chemistry.
• Cp*Ir(III) species are vital, yet acyclic types lag behind cyclic ones in development.
• Acyclic Cp*Ir(III) complexes require efficient synthetic strategies.

Purpose of the Study:

• To develop a general and efficient synthesis for acyclic aryl Cp*Ir(III)(CO)Cl complexes.
• To explore the reactivity and stability of these novel acyclic complexes.
• To establish a platform for advancing acyclic Cp*Ir(III) chemistry.

Main Methods:

• Synthesis of aryl Cp*Ir(III)(CO)Cl complexes from aryl aldehydes using in situ generated CO.
• Investigation of reactivity with eight classes of nucleophiles.
• Electrochemical analysis to study reductive elimination processes.
• Development of Cp*Ir(III)-mediated decarbonylative cross-coupling reactions.

Main Results:

• A general and efficient strategy for synthesizing persistent aryl Cp*Ir(III)(CO)Cl complexes was established.
• These acyclic complexes demonstrated exceptional reactivity with diverse nucleophiles, forming stable diorganoiridium(III) species.
• Insights into reductive elimination processes were gained through electrochemical analysis.
• Cp*Ir(III)-mediated decarbonylative C-C and C-O cross-couplings of aryl aldehydes were successfully developed.

Conclusions:

• The study presents a robust synthetic platform for acyclic Cp*Ir(III) complexes.
• The developed complexes offer remarkable stability and reactivity, opening new avenues in iridium chemistry.
• This work significantly advances the field of acyclic Cp*Ir(III) complex development and application.