Synthesis of Fused Metallaaromatics via Intramolecular C–H Activation of Thiophenes

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• 作者：Qingde Zhuo ; Xiaoxi Zhou ; Huijun Kang ; Zhiyong Chen ; Yuhui Yang ; Feifei Han ; Hong Zhang ; Haiping Xia
• 刊名：Organometallics
• 出版年：2016
• 出版时间：May 23, 2016
• 年：2016
• 卷：35
• 期：10
• 页码：1497-1504
• 全文大小：513K
• 年卷期：0
• ISSN：1520-6041

文摘

A convenient method to synthesize novel fused ruthena-/osmacycles via intramolecular C–H activation of thiophenes has been developed. Treatment of HC≡CCH(OH)R (R = 2-thienyl) with RuCl₂(PPh₃)₃ or OsCl₂(PPh₃)₃ afforded hydroxyl-coordinated metal vinyl compounds 1 and 4. Reaction of 1/4 with acid produced metal alkenylcarbene complexes 3/5, which can further convert to the corresponding fused metallaaromatics 2/7 via the C(sp²)–H activation of the thienyl groups. 7 is the first example of a metallabenzyne with a fused five-membered ring (thiophene ring). These fused metallaaromatics are thermally stable both in solution and in the solid state in air. The X-ray crystallographic analysis, NMR spectra, and DFT calculations all suggest that these fused metallaaromatics (2 and 7) show aromatic character.