Synthesis and Characterization of Lithium Hemiporphyrazines

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• 作者：Saovalak Sripothongnak ; Anna M. Pischera ; Matthew P. Espe ; William S. Durfee ; Christopher J. Ziegler
• 刊名：Inorganic Chemistry
• 出版年：2009
• 出版时间：February 16, 2009
• 年：2009
• 卷：48
• 期：4
• 页码：1293-1300
• 全文大小：228K
• 年卷期：v.48,no.4(February 16, 2009)
• ISSN：1520-510X

文摘

The hemiporphyrazines comprise a broad class of phthalocyanine analogues where one or two of the diiminoisoindolene units are replaced with alternative rings, including pyridines, benzenes, and azoles. As a means to explore the fundamental metal chemistry of these macrocycles, we have prepared the first lithium complexes of three hemiporphyrazine variants: the common bis-pyridine ring, the bis-benzene macrocycle (also known as dicarbahemiporphyrazine), and the monobenzene variant (also known as benziphthalocyanine). The metal cation can be inserted via reaction of the free bases by using lithium bis(trimethylsilyl)amide, and the resulting products all form 1:1 complexes with protonation at the meso nitrogens providing charge balance. For the two carbahemiporphyrazines studied, the internal C−H bond remains intact upon metalation. Similar structures have been observed in the transition metal complexes of the carbaporphyrins. In addition, all three complexes are characterized by ⁷Li solid state NMR and by cyclic voltammetry.