Direct Characterization of Metal–Metal Bonds between Nuclei with Strong Quadrupolar Interactions via NMR Spectroscopy

Metal–metal bonds can be difficult to characterize directly. We demonstrate that <i>J</i> couplings between metal nuclei experiencing strong quadrupolar interactions can be easily measured from well-defined splittings in NMR spectra of powdered samples. Using ^69/71Ga NMR, it is shown that homonuclear <i>J</i> coupling, which is four orders of magnitude smaller than the quadrupolar coupling in a series of compounds featuring gallium–gallium bonds, can be extracted with a 2-D NMR experiment. The dependence of the multiplets on crystal symmetry reveals information on the structures of two Ga–Ga-bonded compounds for which diffraction data are unavailable. Interpretation of the data in a molecular orbital framework provides insight into the nature of the metal–metal bond