The compound [CP*MO(PMe3)(3)H] (1) is reversibly oxidized at E-1/2 = -1.40 V vs ferrocene in MeCN. Its oxidation with Cp2FePF6 yields thermally stable [Cp*Mo(PMe3)(3)H]PF6 (2), which has been isolated and characterized by IR and EPR spectroscopy and by single-crystal X-ray diffraction. The H-1 and P-31 NMR spectra of 1 show two types of PMe3 ligands in a 1:2 ratio at low temperature, but only one average signal at room temperature, with activation parameters of Delta H-double dagger = 11.7(3) kcal mol(-1) and Delta S-double dagger = -3(1) eu for the exchange process. Although only one species is evidenced by NMR for 1 and by EPR for 2, the solution IR spectra of each complex show two bands in the nu(Mo-H) region (1, major at 1794 cm(-1) and minor at ca. 1730 cm(-1); 2, ca. 1800 and 1770 cm(-1) with approximately equal intensity), the position and relative intensity being little dependent on the solvent. A thorough DFT investigation suggests that these are different rotamers involving different relative orientations of the Cp* ring and the PMe3 ligands in these complexes. This ring rotation process is very rapid on the NMR and EPR time scale but slow on the IR time scale. The X-ray data and the theoretical calculations suggest the presence of weak Mo-H center dot center dot center dot F interactions in compound 2. The possibility of PMe3 dissociation, as well as other intramolecular rearrangements, for 1 and 2 is excluded by experimental and computational studies. Protonation of 1 yields [Cp*Mo(PMe3)(3)H-2](+) (3), which also reveals a dynamic process interconverting the two inequivalent H ligands and the three PMe3 ligands (two sets in a 1:2 ratio in the frozen structure) on the NMR time scale (activation parameters of Delta H double dagger = 9.3(1) kcal/mol and Delta S-double dagger = -4.1(4) eu). A DFT study suggests that this exchange process occurs via a low-energy symmetric dihydride intermediate and not through a dihydrogen complex.