Synthesis, Spectroscopic Properties, and Reactivities of Bis(tosylimido)osmium(VI) Porphyrin Complexes. X-ray Crystal Structure of [OsVI(TPP)(NSO2C6H4-pCH 3)2] (TPP = Tetraphenylporphyrinato)

Abstract

The bis(tosylimido)osmium(VI) porphyrins [OsVI(Por)(NTs)2] [Por = tetraphenylporphyrinato (TPP), meso-tetrakis(p-tolyl)porphyrinato (TTP), meso-tetrakis(4-chlorophenyl)porphyrinato (4-Cl-TPP), weso-tetrakis(4-methoxyphenyl)porphyrinato (4-MeO-TPP); Ts = tosyl] were prepared from the reactions of [OsII(Por)(CO)(MeOH)] with excess PhI=NTs in dichloromethane. The X-ray crystal structure of [OsVI(TPP)(NTs)2] has been determined. Crystal data for [OsVI(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) Å3, Z = 2, R (Rw) = 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 [OsVI(TPP)(NTs)2] with triphenylphosphine gives Ph3P=NTs and [OsII(TPP)(PPh3)2].