双（对甲苯磺酰亚胺基）锇（VI）卟啉配合物的合成、光谱性质及反应活性。[Os(VI)(TPP)(NSO(2)C(6)H(4)-pCH(3))(2)]的X射线晶体结构（TPP = 四苯基卟啉）

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).

作者信息

Au Sze-Man, Fung Wai-Hong, Huang Jie-Sheng, Cheung Kung-Kai, Che Chi-Ming

机构信息

Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong.

出版信息

Inorg Chem. 1998 Dec 28;37(26):6564-6567. doi: 10.1021/ic980256u.

DOI:10.1021/ic980256u

PMID:11670787

Abstract

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)].

摘要

双（对甲苯磺酰亚胺）锇（VI）卟啉[Os(VI)(Por)(NTs)(2)] [Por = 四苯基卟啉（TPP）、中位四（对甲苯基）卟啉（TTP）、中位四（4-氯苯基）卟啉（4-Cl-TPP）、中位四（4-甲氧基苯基）卟啉（4-MeO-TPP）；Ts = 对甲苯磺酰基] 由[Os(II)(Por)(CO)(MeOH)]与过量的PhI=NTs在二氯甲烷中反应制备得到。已测定[Os(VI)(TPP)(NTs)(2)]的X射线晶体结构。[Os(VI)(TPP)(NTs)(2)]的晶体数据：三斜晶系，空间群P&onemacr;（编号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) Å(3)，Z = 2，R（R(w)） = 0.030（0.038），拟合优度 = 1.19。Os=NTs的平均距离为1.800 Å。Os-N-S角平均为155.8°。[Os(VI)(TPP)(NTs)(2)]与三苯基膦反应生成Ph(3)P=NTs和[Os(II)(TPP)(PPh(3))(2)]。