Reaction of Tp*(MoSCl2)-S-V with a variety of phenols and thiols in the presence of triethylamine produces mononuclear, thiomolybdenyl complexes Tp*(MoSX2)-S-V [Tp* = hydrotris(3,5-dimethylpyrazol-1-yl)borate; X = 2-(ethylthio)phenolate (etp), 2-(n-propyl)phenolate (pp), phenolate; X-2 = benzene-1,2-dithiolate (bdt), 4-methylbenzene-1,2-dithiolate (tdt), benzene-1,2-diolate (cat)]. The complexes have been characterized by microanalysis, mass spectrometry, IR, EPR, and UV-visible spectroscopic data, and X-ray crystallography (for the etp, pp, bdt, and cat derivatives). The mononuclear, six-coordinate, distorted-octahedral Mo centers are coordinated by terminal sulfido (Mo=S = 2.123(1)-2.1368(8) angstrom), tridentate facial Tp*, and monodentate or bidentate O/S-donor ligands. Multifrequency (S-, X-, Q-band) EPR spectra of the complexes and selected molybdenyl analogues were acquired at 130 K and 295 K and yielded a spin Hamiltonian of C-s symmetry or lower, with g(zz) < g(yy) < g(xx) < g(e) and A(z'z') > A(x'x') approximate to A(y'y'), and a noncoincidence angle in the range of beta = 24-39 degrees. Multifrequency EPR, especially at S-band, was found to be particularly valuable in the unambiguous assignment of the spin Hamiltonian parameters in these low-symmetry complexes. The weaker pi-donor terminal sulfido ligand yields a smaller SOMO-LUMO gap and reduced g-values for the thiomolybdenyl complexes compared with molybdenyl analogues, supporting existing crystallographic and EPR data for an apically coordinated oxo group in the active site of xanthine oxidase.