Using a combination of solid-state NMR techniques including Tip measurements, dynamic line shape analyses and 2D EXSY data, a variety of intramolecular motions including rotations of methyl, t-butyl, t-amyl, phenyl, trimethylammonium and trimethylphosphonium groups in a series of quaternary ammonium and phosphonium salts have been investigated. Where possible, activation parameters Ea, △G+/-, △H+/- and △S+/- have been derived. A range of values was recorded, especially for △S+/- which ranged from +75 JK−1 mol−1 for a phenyl group to -57 JK−1 mol−1for a t-butyl group. It was shown that 13p and 31p T1p measurements from CP/MAS spectra can give quantitative information on the kinetics of intramolecular motions that agree with line shape analysis. Recent work using X-ray crystallography has suggested that some derivatives of bicycle [3.3.1] nonane show evidence of conformational equilibria in the solid state. Using 13CP/MAS NMR, 22 derivatives of bicycle [3.3.1] nonane were studied, some at variable temperature. No evidence of conformational equilibria was observed in the chosen compounds. Solid-state NMR has been used to follow the kinetics of ring- chain tautomerism in a bicyclic tetrahydro-1,3-oxazine derivative. This was found to form initially the metastable chain on crystallisation, which then cyclises. The kinetics of the cyclisation were followed and the activation energy for the solid-state reaction was derived. In contrast to this, a related pyrimidine derivative has been found to form initially the metastable ring on cyclisation which quickly ring opens to the chain.