Effect of Ancillary Ligand on Electronic Structure as Probed by ⁵¹V Solid-State NMR Spectroscopy for...

A series of vanadium(V) complexes with o-dioxolene (catecholato) ligands and an ancillary ligand, (N-(salicylideneaminato)ethylenediamine) (hensal), were investigated using ⁵¹V solid-state magic angle spinning NMR spectroscopy (⁵¹V MAS NMR) to assess the local environment of the vanadium(V). The solid-state ⁵¹V NMR parameters of vanadium(V) complexes with a related potentially tetradentate ancillary ligand (N-salicylidene-N'-(2-hydroxyethyl)ethylenediamine) (h₂shed) were previously shown to be associated with the size of the HOMO-LUMO gap in the complex, and as such provide insights on the interaction between metal ion and ligand (P. B. Chatterjee, et al., Inorg. Chem 50 (2011) 9794). Our results show that the modification of the ancillary ligand does not impact the observed trend between complexes ranging from catechols with electron rich to electron poor substituents. However, the ancillary ligand does impact the size of the HOMO-LUMO separation in the parent complex and thus the solid-state vanadium NMR chemical shift of the unsubstituted vanadium complex. For these complexes significant changes observed in the isotropic shifts and more modest changes detected in the C reflect the electronic changes in the complex as the catechol is varied. However, no obvious trend was observed in the chemical shift anisotropies (δ_σ and η_σ) with the variation in the catechol. The electronic changes in the coordination environment of the vanadium can be described using solid-state ⁵¹V NMR spectroscopy.