Leveraging LMCT manifolds for the development of new catalytic cross-coupling reactions

The recent renaissance of cross-coupling reactions catalyzed by first row transition metals has brought on a major revolution in synthetic organic chemistry. Indeed, the ability of these metals to undergo single electron transfer (SET) and radical capture has allowed the cross-coupling of novel radical-based organic synthons and opened vast, previously inaccessible, chemical space.2 However, one of the fundamental limitations that plague this field is its reliance on outer-sphere single electron transfer (OSET) mechanisms for the generation of the radical partners, which brings stringent thermodynamical limitations and prevent the generation of highly energetic species.