Synthesis, Spectroscopic Properties, and Reactivities of Bis(tosylimido)osmium(VI) Porphyrin Complexes. X-ray Crystal Structure of [Os^VI(TPP)(NSO₂C₆H₄-pCH₃)₂] (TPP = Tetraphenylporphyrinato)

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 P1̄ (No. 2), a = 10.836(3) Å, b = 12.067(4) Å, c = 19.647(6) Å, α = 94.05(3)°, β = 93.88(3)°, γ = 104.65(3)°, V = 2469(1) ų, Z = 2, R (R_w) = 0.030 (0.038), goodness-of-fit = 1.19. The mean OsNTs distance is 1.800 Å. The Os−N−S angles average 155.8°. Reaction of [Os^VI(TPP)(NTs)₂] with triphenylphosphine gives Ph₃PNTs and [Os^II(TPP)(PPh₃)₂].