La-Activated Bicyclo-oligomerization of Acetylene to Naphthalene

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• 作者：Dilrukshi Hewage ; W. Ruchira Silva ; Wenjin Cao ; Dong-Sheng Yang
• 刊名：Journal of the American Chemical Society
• 出版年：2016
• 出版时间：March 2, 2016
• 年：2016
• 卷：138
• 期：8
• 页码：2468-2471
• 全文大小：274K
• ISSN：1520-5126

文摘

We report the first example of metal-mediated acetylene bicyclopentamerization to form naphthalene in the gas phase. The bicyclic aromatic compound was observed in a complex with La. The La(naphthalene) complex was formed by the reaction of laser-ablated La atoms with acetylene molecules in a molecular beam source and was characterized by mass-analyzed threshold ionization spectroscopy. The bicyclo-oligomerization reaction occurs through sequential acetylene additions coupled with dehydrogenation. Three intermediates in the reaction have been identified: lanthanacyclopropene [La(C₂H₂)], La(cyclobut-1-en-3-yne) [La(C₄H₂)], and La(benzyne) [(La(C₆H₄)]. The metal–ligand bonding in the three intermediates is considerably different from that in the La(naphthalene) complex, as suggested by accurately measured adiabatic ionization energies.