(H-1, Rh-103) and (H-1, Rh-103){H-2} inverse correlation techniques, which profit from the presence of a magnetically active central metal nucleus, were applied to the complex [RhY2(Y2){HB(3,5-Me2pz)3}] (Y = H or D; pz = pyrazolyl) containing both 'classical' and 'non-classical' hydrogen ligands. The sample examined was a mixture of all species ranging from the perprotio to the perdeuterio compound. It is shown that the large isotope chemical shifts of the Rh nucleus can be used to separate the 1D H-1 and H-1{H-2} NMR spectra of the different H/D isotopomers. The observed isotope effects are discussed.