Isomerization Reactions in Anionic Mesoionic Carbene‐Borates and Control of Properties and Reactivities in the Resulting CoII Complexes through Agostic Interactions

We present herein anionic borate‐based bi‐mesoionic carbene compounds of the 1,2,3‐triazol‐4‐ylidene type that undergo C?N isomerization reactions. The isomerized compounds are excellent ligands for Co^II centers. Strong agostic interactions with the “C?H”‐groups of the cyclohexyl substituents result in an unusual low‐spin square planar Co^II complex, which is unreactive towards external substrates. Such agostic interactions are absent in the complex with phenyl substituents on the borate backbone. This complex displays a high‐spin tetrahedral Co^II center, which is reactive towards external substrates including dioxygen. To the best of our knowledge, this is also the first investigation of agostic interactions through single‐crystal EPR spectroscopy. We conclusively show here that the structure and properties of these Co^II complexes can be strongly influenced through interactions in the secondary coordination sphere. Additionally, we unravel a unique ligand rearrangement for these classes of anionic mesoionic carbene‐based ligands.