The electronic structures of a series of high-spin Ni(II)-thiolate complexes of the form [PhTt(tBu)]Ni(SR) (R = CPh3, 2; C6F5, 3; C6H5, 4; PhTt(tBu) = phenyltris((tert-butylthio)methyl)borate) have been characterized using a combined spectroscopic and computational approach. Resonance Raman (rR) spectroscopic data reveal that the nu(Ni-SR) vibrational feature occurs between 404 and 436 cm(-1) in these species. The corresponding rR excitation profiles display a striking de-enhancement behavior because of interference effects involving energetically proximate electronic excited states. These data were analyzed in the framework of time-dependent Heller theory to obtain quantitative insight into excited state nuclear distortions. The electronic absorption and magnetic circular dichroism spectra of 2-4 are characterized by numerous charge transfer (CT) transitions. The dominant absorption feature, which occurs at similar to 18,000 cm(-1) in all three complexes, is assigned as a thiolate-to-Ni CT transition involving molecular orbitals that are of pi -symmetry with respect to the Ni-S bond, reminiscent of the characteristic absorption feature of blue copper proteins. Density functional theory computational data provide molecular orbital descriptions for 2-4 and allow for detailed assignments of the key spectral features. A comparison of the results obtained in this study to those reported for similar Ni-thiolate species reveals that the supporting ligand plays a secondary role in determining the spectroscopic properties, as the electronic structure is primarily determined by the metal -thiolate bonding interaction.