Symmetry and the ordering of the inversion and isolated rotation barriers can render inversion "NMR-invisible" in many simple amines, such as all dimethylamino compounds. NMR-invisible processes in RCH(2)NR’R’ amines can be revealed through NMR isotope shifts if the methylene is monodeuteriated to create a chiral center that makes the R’ groups diastereotopic. A Delta G(double dagger) of 8.2 kcal mol(-1) for inversion in N,N-dimethylpentanamine-1-d(1) was found through complete DNMR line-shape analysis of the N-methyl signals in 75 MHz C-13{H-1} spectra. A barrier of 9.5 kcal mol(-1) for the exchange process in N,N-diethyl-2,2-dimethylpropanamine, 3, was found from both H-1 spectra of 3 and C-13 spectra of 3-d(1). The barrier for 3 is higher than expected for inversion and can be explained by inversion of a conformation that has a nearly eclipsing neopentyl group to a conformation that has a high barrier for a rotation to complete the exchange process.