Dynamic nuclear polarization surface-enhanced nuclear magnetic resonance (NMR) spectroscopy has enabled the determination of the three-dimensional configuration of surface sites, in particular supported metal complexes of relevance to single-site heterogeneous catalysis. These approaches have chiefly leveraged the application of NMR double-resonance experiments that either reveal the complex conformation via point-to-point intramolecular distances between spin-labeled atoms or the complex-surface orientation via distances between the spins and the surface plane. Either method typically requires expensive isotope labeling and each reports on different structural features. The application of an experiment that simultaneously reveals both types of distances with chemical resolution would be ideal. In this article, we describe an 17O{1H} pseudo-3D correlation experiment that achieves this goal. Specifically, Si–O–Si and Si–O–M oxygens are well-resolved by 17O NMR; therefore, distances can be simultaneously measured radially, between Si–17O–M and the 1H’s of the ligands, and vertically to the Si–17O–Si linkages of the silica support. We demonstrate the experiment using supported yttrium and zirconium complexes. Good agreement is obtained when comparing the experimental results to theoretical predictions from density functional theory calculations, highlighting the reliability of this relatively simple experiment.

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Single atom, low valent transition metals are important for heterogeneous catalysis but are challenging to generate and stabilize in a well-defined manner. Herein, we explored the functionalization of...