The first chromium-53 solid-state nuclear magnetic resonance spectra of diamagnetic chromium(0) and chromium(VI) compounds

Chromium-53 is a spin-3/2 nucleus with a relatively small magnetic moment, low natural abundance, and large quadrupole moment. These properties have severely hampered the development of 53Cr NMR, especially in the solid state. In this Communication, the first 53Cr solid-state NMR spectra of prototypal diamagnetic chromium(0) and chromium(VI) compounds are presented. Specifically, analyses of 53Cr NMR spectra of solid hexacarbonylchromium(0), caesium chromate(VI), and potassium chromate(VI) have allowed for the determination of 53Cr quadrupolar coupling parameters and the first chromium chemical shift (CS) tensors. This work demonstrates the potential of 53Cr solid-state NMR, in particular the extreme sensitivity of the 53Cr quadrupolar coupling constant to the local chromium environment. Comparisons are made to known 53Cr NMR parameters available from solution studies, and to the 95Mo solid-state NMR parameters of analogous molybdenum compounds. The influence of crystal symmetry present in isomorphic Cr(CO)6 and Mo(CO)6 is strongly reflected in the magnitudes of the metal nuclei CS tensors and in their orientation with respect to their corresponding electric field gradient tensors.