Electronic Structures of Late versus Early Transition Metal Imido Complexes from ¹⁵ N‐NMR Signatures

Abstract Imido ligand is a ubiquitous motif in organometallic chemistry, serving roles spanning from ancillary ligands to reactive sites. The nature of M=N bond is highly depended on the metal centres and their d‐electron configuration, with late transition metal (TM) imido complexes exhibiting contrasting features when compared to their early TM analogues. Envisioning to uncover general electronic descriptor for the nature of imido ligands, we computationally investigate the solid‐state 15 N NMR signatures of late TM imido complexes with various central metals, geometries and d‐electron counts, and compare them against these of the corresponding early TM systems. The spectroscopic signatures are mostly driven by the presence of filled, π‐symmetry orbitals in late TM imido complexes, suggesting the development of high‐lying π(M=N) and low‐lying σ/σ * (M=N) orbitals. This contrasts with what is observed for the reported early TM systems, for which high‐lying σ‐type orbitals determine the NMR signature. Noteworthily, Ni‐ and Pd‐imido complexes with formal d 10 configurations exhibit highly asymmetric nitrogen‐15 NMR signature with extremely deshielded principal components, because of the presence of filled, high‐lying antibonding π * (M=N) orbitals, consistent with their high reactivity. The sensitive response of 15 N NMR signature to the nature of metal sites further highlights that chemical shift is a useful reactivity descriptor.