Synthesis and Characterization of Palladium(II) Complexes of meso-Substituted [14]Tribenzotriphyrin(2.1.1)

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• 作者：Zhaoli Xue ; Yemei Wang ; John Mack ; Yuanyuan Fang ; Zhongping Ou ; Weihua Zhu ; Karl M. Kadish
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：December 21, 2015
• 年：2015
• 卷：54
• 期：24
• 页码：11852-11858
• 全文大小：407K
• ISSN：1520-510X

文摘

Metalation of 6,13,20,21-tetrakis-aryl-22H-[14]tribenzotriphyrin(2.1.1) (TriPs) with PdCl₂ provides Pd^II鈥揟riP complexes in 45鈥?6% yields. The complexes were characterized by mass spectrometry, and UV鈥搗isible absorption, magnetic circular dichroism, and ¹H NMR spectroscopy. A single crystal X-ray analysis reveals that the Pd^II鈥揟riPs adopts a deeply saddled conformation. The palladium(II) ion is coordinated by two pyrrole nitrogen atoms and two chloride ions to form the square-planar coordination environment. The redox properties of the Pd^II鈥揟riPs were studied by cyclic voltammetry. Each compound undergoes one irreversible and two reversible one-electron reductions. There is a marked red-shift of the main spectral bands, relative to those of the free-base TriP ligand, due to a marked relative stabilization of the LUMO upon coordination by PdCl₂.