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

24 October 2024, Version 2
This content is a preprint and has not undergone peer review at the time of posting.

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 15N 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 d10 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 15N NMR signature to the nature of metal sites further highlights that chemical shift is a useful reactivity descriptor.

Keywords

Imido complex
15N NMR spectroscopy
solid-state NMR
electronic structure

Supplementary materials

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Description
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Supporting Information
Description
Computational details, calculated NMR parameters and summary of NCS analysis.
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xyz files
Description
xyz coordinates of the complexes investigated herein.
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