The insertion reaction of Cu-H is a key elementary step in many proposed catalytic cycles for the hydrofunctionalization of olefinic and carbonylic substrates. Yet, the details of the insertion step of Cu-H are lacking due to their rapid decomposition in solution, making systematic and quantitative studies difficult. We now report mechanistic studies on the insertion of Cu-H complexes ligated by bulky imidazolinylidene and ring-expanded NHCs of the type [(NHC)Cu]2(μ-H)2] (NHC = IPr*, 6SIPr, 7SIPr) with aldehyde, ketone, activated ester/amide, and unactivated amide substrates. Results from mechanistic studies showed two distinct rate limiting steps (equilibrium control and hydride transfer) for the insertion reactions. These observations have allowed us to map reaction schemes for the migratory insertion of [(NHC)Cu]2(μ-H)2] with different carbonyl derivatives.

Mechanistic divergence for the insertion reaction of Cu-H dimer with polar carbonyl substrates: Effect of electrophilicity and steric influence of NHCs

Macromolecular Chemistry: The Second Century

[Author Benefits](https://scimeetings.acs.org/?utm_source=pubs_content_marketing&utm_medium=website&utm_campaign=0320_MCF_NPI_Launch_Spring_Homepage&ref=pubs_content_marketing)

[How to use SciMeetings](https://storage.googleapis.com/dl.morressier.com/acs/SciMeetings-ACSSpring2020-HowToGuide_M3020-Final.pdf)

[Frequently Asked Questions](https://storage.googleapis.com/dl.morressier.com/acs/SciMtng_ACSNMSp2020_FAQ_M3120_Final.pdf)

ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.