Novel Thiophene-Based Cycloruthenated Compounds: Synthesis, Characterization, and Reactivity

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• 作者：Luciano Cuesta ; Irene Maluenda ; Tatiana Soler ; Rafael Navarro ; Esteban P. Urriolabeitia
• 刊名：Inorganic Chemistry
• 出版年：2011
• 出版时间：January 3, 2011
• 年：2011
• 卷：50
• 期：1
• 页码：37-45
• 全文大小：966K
• 年卷期：v.50,no.1(January 3, 2011)
• ISSN：1520-510X

文摘

The reactions between a series of thiophene-based imines with [(畏⁶-C₆H₆)RuCl(渭-Cl)]₂, in a basic medium, and in MeCN give a family of ruthenacycles of stoichiometry [Ru(CN)(NCMe)₄]PF₆ (CN = orthometalated thiopheneimine). In these species, the C鈭扝 activation process is produced in most cases at the thiophene ring. When two C鈭扝 bonds are competing (thiophene vs aryl), the cyclometalation can be driven regioselectively to the thiophene unit or to the aryl ring as a function of the location of the iminic C鈺怤 bond. Cyclometalation can also be oriented to positions 2 or 3 of the thiophene depending on the situation of the imine in the heterocycle (3 or 2, respectively). In all studied cases, the 畏⁶-C₆H₆ ligand was substituted by acetonitrile. The X-ray structures of two representative complexes have been determined. These thiophene-based metallacycles react with iodine under very mild conditions affording, after hydrolysis, substituted 3-iodo-2-formyl(benzo)thiophenes or substituted 2-iodo-3-formyl(benzo)thiophenes, as a function of the organometallic precursor.