La-Activated Bicyclo-oligomerization of Acetylene to Naphthalene

Dilrukshi Hewage; W. Ruchira Silva; Wenjin Cao; Dong Sheng Yang

doi:10.1021/jacs.5b08657

La-Activated Bicyclo-oligomerization of Acetylene to Naphthalene

Dilrukshi Hewage, W. Ruchira Silva, Wenjin Cao, Dong Sheng Yang

Chemistry

Research output: Contribution to journal › Article › peer-review

30 Scopus citations

Abstract

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.

Original language	English
Pages (from-to)	2468-2471
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	138
Issue number	8
DOIs	https://doi.org/10.1021/jacs.5b08657
State	Published - Mar 2 2016

Bibliographical note

Funding Information:
We are grateful for the financial support from the National Science Foundation, Division of Chemistry (Chemical Structure, Dynamics, and Mechanisms, Grant CHE-1362102). We also acknowledge additional support from the Kentucky Science and Engineering Foundation. We thank Jack Selegue for helpful discussions about possible reaction pathways for the cyclopentamerization of acetylene.

Publisher Copyright:
© 2016 American Chemical Society.

ASJC Scopus subject areas

Catalysis
Chemistry (all)
Biochemistry
Colloid and Surface Chemistry

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title = "La-Activated Bicyclo-oligomerization of Acetylene to Naphthalene",

abstract = "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.",

author = "Dilrukshi Hewage and Silva, {W. Ruchira} and Wenjin Cao and Yang, {Dong Sheng}",

note = "Funding Information: We are grateful for the financial support from the National Science Foundation, Division of Chemistry (Chemical Structure, Dynamics, and Mechanisms, Grant CHE-1362102). We also acknowledge additional support from the Kentucky Science and Engineering Foundation. We thank Jack Selegue for helpful discussions about possible reaction pathways for the cyclopentamerization of acetylene. Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

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doi = "10.1021/jacs.5b08657",

language = "English",

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AU - Hewage, Dilrukshi

AU - Silva, W. Ruchira

AU - Cao, Wenjin

AU - Yang, Dong Sheng

N1 - Funding Information: We are grateful for the financial support from the National Science Foundation, Division of Chemistry (Chemical Structure, Dynamics, and Mechanisms, Grant CHE-1362102). We also acknowledge additional support from the Kentucky Science and Engineering Foundation. We thank Jack Selegue for helpful discussions about possible reaction pathways for the cyclopentamerization of acetylene. Publisher Copyright: © 2016 American Chemical Society.

PY - 2016/3/2

Y1 - 2016/3/2

N2 - 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.

AB - 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.

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La-Activated Bicyclo-oligomerization of Acetylene to Naphthalene

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