Huang Jie-Sheng, Leung Sarana Ka-Yan, Zhou Zhong-Yuan, Zhu Nianyong, Che Chi-Ming
Department of Chemistry and Open Laboratory of Chemical Biology of the Institute of Molecular Technology for Drug Discovery and Synthesis, The University of Hong Kong, Pokfulam Road, Hong Kong.
Inorg Chem. 2005 May 30;44(11):3780-8. doi: 10.1021/ic0484102.
Reaction of dioxoruthenium(VI) porphyrins [Ru(VI)(Por)O2] with arylimine HN=CPh2 in dichloromethane afforded bis(methyleneamido)ruthenium(IV) porphyrins [Ru(IV)(Por)(N=CPh2)2] for Por = 4-Cl-TPP and TMP; (methyleneamido)hydroxoruthenium(IV) porphyrins [Ru(IV)(Por)(N=CPh2)(OH)] for Por = TPP and TTP; and bis(arylimine)ruthenium(II) porphyrins [Ru(II)(Por)(HN=CPh2)2] for Por = 3,5-Cl2TPP and 3,5-(CF3)2TPP. In dichloromethane solution exposed to air, complex [Ru(II)(3,5-Cl2TPP)(HN=CPh2)2] underwent oxidative deprotonation to form [Ru(IV)(3,5-Cl2TPP)(N=CPh2)2]. The new ruthenium porphyrins were identified by 1H NMR, UV-vis, IR, and mass spectroscopy, along with elemental analysis. X-ray crystal structure determinations of [Ru(IV)(4-Cl-TPP)(N=CPh2)2], [Ru(IV)(TPP)(N=CPh2)(OH)], and [Ru(II)(3,5-(CF3)2TPP)(HN=CPh2)2] revealed the Ru-N(methyleneamido) or Ru-N(arylimine) distances of 1.897(5) A (average), 1.808(4) A, and 2.044(2) A (average), respectively.
在二氯甲烷中，二氧钌（VI）卟啉[Ru(VI)(Por)O₂]与芳基亚胺HN = CPh₂反应，对于Por = 4-Cl-TPP和TMP，生成双（亚甲基氨基）钌（IV）卟啉[Ru(IV)(Por)(N = CPh₂)₂]；对于Por = TPP和TTP，生成（亚甲基氨基）羟基钌（IV）卟啉[Ru(IV)(Por)(N = CPh₂)(OH)]；对于Por = 3,5-Cl₂TPP和3,5-(CF₃)₂TPP，生成双（芳基亚胺）钌（II）卟啉[Ru(II)(Por)(HN = CPh₂)₂]。在暴露于空气的二氯甲烷溶液中，配合物[Ru(II)(3,5-Cl₂TPP)(HN = CPh₂)₂]发生氧化去质子化反应，形成[Ru(IV)(3,5-Cl₂TPP)(N = CPh₂)₂]。通过¹H NMR、紫外可见光谱（UV-vis）、红外光谱（IR）、质谱以及元素分析对新的钌卟啉进行了鉴定。[Ru(IV)(4-Cl-TPP)(N = CPh₂)₂]、[Ru(IV)(TPP)(N = CPh₂)(OH)]和[Ru(II)(3,5-(CF₃)₂TPP)(HN = CPh₂)₂]的X射线晶体结构测定结果表明，Ru-N（亚甲基氨基）或Ru-N（芳基亚胺）的距离分别为1.897(5) Å（平均值）、1.808(4) Å和2.044(2) Å（平均值）。
