The RSRS and RRSS isomers of [Ni(tmc)](OTf)2 (tmc = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane; OTf(-) = CF3SO3-) react with NaSC6H5 to yield the corresponding high spin, five-coordinate derivatives, [Ni(tmc)SC6H5](OTf). The molecular structure of each has been determined by X-ray diffraction. RRSS-[Ni(tmc)SC6H5](OTf) crystallized in the monoclinic space group P2(1)/n, with a = 12.648(3) Angstrom, b = 15.145(4) Angstrom, c = 14.765(4) Angstrom, beta = 113.96(2)degrees, V = 2584(1) Angstrom(3), and Z = 4. The coordination sphere about Ni is best described as square pyramidal with a Ni-S bond distance of 2.369(2) Angstrom and Ni-N-av of 2.128 Angstrom. RSRS-[Ni(tmc)SC6H5]-(PF6) crystallized in the monoclinic space group P2(1)/n, with a = 13.037(5) Angstrom, b = 15.407(7) Angstrom, c = 13.706(7) Angstrom, beta = 113.53(3)degrees, V = 2524(2) Angstrom(3), and Z = 4. The Ni resides in a highly distorted square pyramid with a shorter Ni-S distance, 2.352(2)Angstrom and correspondingly longer Ni-N-av distance of 2.149 Angstrom. Alternatively [Ni(tmc)SR](OTf) may be produced by oxidative addition of disulfide, R(2)S(2) (R = C6H5, C2H5), to Ni(tmc)(OTf).