Synthesis, Spectroscopic Properties, and Reactivities of Bis(tosylimido)osmium(VI) Porphyrin Complexes. X-ray Crystal Structure of [Os(VI)(TPP)(NSO(2)C(6)H(4)-pCH(3))(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 P&onemacr; (No. 2), a = 10.836(3) Å, b = 12.067(4) Å, c = 19.647(6) Å, alpha = 94.05(3) degrees, beta = 93.88(3) degrees, gamma = 104.65(3) degrees, V = 2469(1) Å(3), 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 degrees. Reaction of [Os(VI)(TPP)(NTs)(2)] with triphenylphosphine gives Ph(3)P=NTs and [Os(II)(TPP)(PPh(3))(2)].
Au
Sze-Man
SM
Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong.
Fung
Wai-Hong
WH
Huang
Jie-Sheng
JS
Cheung
Kung-Kai
KK
Che
Chi-Ming
CM