<b>Abstract: </b>Square-planar cobalt(II)-systems have emerged as powerful carbene transfer catalysts for the synthesis of a variety of (hetero)cyclic compounds via redox non-innocent Co(III)-carbene radical intermediates. Spectroscopic detection and characterization of these reactive carbene radical intermediates has thus far been limited to a few scattered experiments, in part due to the fact that most studies have focused on mono-substituted carbene precursors. In this work, we demonstrate the unique formation of disubstituted cobalt(III)-carbene radicals in reactions between a cobalt(II)-porphyrin com-plex with acceptor-acceptor iodaneylidenes (iodonium ylides) as the carbene precursors. We report detailed spectroscopic characterization of the resulting reactive carbene radical species, and their application in styrene cyclopropanation. In particular, we demonstrate that iodonium ylides generate novel bis-carbenoid species leading to reversible substrate-promoted ligand modification of the commercially available [Co(TPP)]-catalyst. Two interconnected catalytic cycles are involved in the overall catalytic reaction with a mono-terminal carbene radical and an unprecedented N-enolate-carbene radical intermediate as the respective key species for the mono- and bis-carbene cycles. Notably, N-enolate formation is not a catalyst deactivation pathway, and both the N-enolate and the carbene radical moieties can be transferred as carbene units to styrene. The studies provide a detailed picture of the new [Co(TPP)]-catalyzed carbene transfer reactions from iodonium ylides. The findings are supported by detailed and unequivocal characterization of the reactive N-enolate & carbene radical intermediates and their deactivation products (EPR, UV-Vis, HR-MS, NMR, in-situ ATR-FT-IR, SC-XRD), Hammett analysis, mechanistic control experiments, DFT reaction pathway profiling and NEVPT2-CASSCF electronic structure calculations.<br>
[Co(TPP)]–Catalyzed Carbene Transfer from Acceptor–Acceptor Iodonium Ylides via N-enolate Carbene Radicals
