Several derivatives of the pseudotetrahedral phenylthiolate complex Tp(Me,Me) Ni-SPh (1), Tp(Me,Me-) = hydrotris(3,5-dimethyl-1-pyrazolyl) borate, were prepared incorporating substituted arylthiolates, including a series of orthosubstituted ligands Tp(Me,Me)Ni-SR (R = 2,6-Me2C6H3, 2: 2,4,6-Me3C6H2, 3; 2,4,6- (Pr3C6H2)-Pr-i, 4; and 2,6-Ph2C6H3, 5) and a series of para-substituted complexes (R = C6H4-4-OMe, 6; C6H4-4-Me, 7; and C6H4-4-Cl, 8). The products were characterized by H-1 NMR and UV-vis spectroscopy. Spectra of 6-8 were consistent with retention of a common structure across the para-substituted series with modest perturbation of the spectral features of 1 assisting their assignment. In contrast, spectra of 2-5 were indicative of a significant change in configuration across the ortho-disubstituted series. The structure of complex 5 was determined by X-ray crystallography and a distinctive arylthiolate ligation mode was found, in which the N3S ligand field was significantly distorted toward a sawhorse, compared to a more common trigonal pyramidal shape (e.g., 1). Moreover, the arylthiolate substituent rotated from a vertical orientation co-directional with the pyrazole rings and disposed between two of them in 1, to a horizontal orientation perpendicular to and over a single pyrazole ring in 5. This reorientation is necessary to accommodate the large ortho substituents of the latter complex. The divergent Ni-S coordination modes result in distinct H-1 NMR and electronic spectra that were rationalized by density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations. These results demonstrate rich coordination chemistry for arylthiolates that can be elicited by steric manipulation at the periphery of pseudotetrahedral ligand fields.