NMR Crystallography Enhanced by Quantum Chemical Calculations and Liquid State NMR Spectroscopy for the Investigation...

N-heterocyclic carbene ligands (NHC) are widely utilized in catalysis and material science. They are characterized by their steric and electronic properties. Steric properties are usually quantified on the basis of their static structure, which can be determined by X-ray diffraction. The electronic properties are estimated in the liquid state; for example, via the ⁷⁷ Se liquid state NMR of Se-NHC adducts. We demonstrate that ⁷⁷ Se NMR crystallography can contribute to the characterization of the structural and electronic properties of NHC in solid and liquid states. Selected Se-NHC adducts are investigated via ⁷⁷ Se solid state NMR and X-ray crystallography, supported by quantum chemical calculations. This investigation reveals a correlation between the molecular structure of adducts and NMR parameters, including not only isotropic chemical shifts but also the other chemical shift tensor components. Afterwards, the liquid state ⁷⁷ Se NMR data is presented and interpreted in terms of the quantum chemistry modelling. The discrepancy between the structural and electronic properties, and in particular the π-accepting abilities of adducts in the solid and liquid states is discussed. Finally, the ¹³ C isotropic chemical shift from the liquid state NMR and the ¹³ C tensor components are also discussed, and compared with their ⁷⁷ Se counterparts. ⁷⁷ Se NMR crystallography can deliver valuable information about NHC ligands, and together with liquid state ⁷⁷ Se NMR can provide an in-depth outlook on the properties of NHC ligands.