The bis(tosylimido)osmium(VI) porphyrins [Os-VI(Por)(NTs)(2)] [Por = tetraphenylporphyrinato (TPP), meso-tetrakis(p-tolyl)porphyrinato (TTP), meso-tetrakis(4-chlorophenyl)porphyrinato (4-Cl-TPP), meso-tetrakis(4-methoxyphenyl)porphyrinato (4-MeO-TPP); Ts = tosyl] were prepared from the reactions of [Os-II(Por)(CO)(MeOH)] with excess PhI=NTs In dichloromethane. The X-ray crystal structure of [Os-VI(TPP)(NTs)(2)] has been determined. Crystal data for [Os-VI(TPP)(NTs)(2)]: triclinic, space group (No. 2), a = 10.836(3) Angstrom, b = 12.067(4) Angstrom, c = 19.647(6) Angstrom, alpha = 94.05(3)degrees, beta = 93.88(3)degrees, gamma = 104.65(3)degrees V= 2469(1) Angstrom(3), Z = 2, R (R-w) = 0.030 (0.038), goodness-of-fit = 1.19. The mean Os=NTs distance is 1.800 Angstrom. The Os-N-S angles average 155.8 degrees. Reaction of [Os-VI(TPP)(NTs)(2)] with triphenylphosphine gives Ph3P=NTs and [Os-II(TPP)(PPh3)(2)].