Spectroscopy and formation of lanthanum-hydrocarbon radicals formed by association and carbon-carbon bond cleavage of isoprene

Wenjin Cao; Dilrukshi Hewage; Dong Sheng Yang

doi:10.1063/1.5026899

Spectroscopy and formation of lanthanum-hydrocarbon radicals formed by association and carbon-carbon bond cleavage of isoprene

Wenjin Cao, Dilrukshi Hewage, Dong Sheng Yang

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

4 Scopus citations

Abstract

La atom reaction with isoprene is carried out in a laser-vaporization molecular beam source. The reaction yields an adduct as the major product and C - C cleaved and dehydrogenated species as the minor ones. La(C₅H₈), La(C₂H₂), and La(C₃H₄) are characterized with mass-analyzed threshold ionization (MATI) spectroscopy and quantum chemical computations. The MATI spectra of all three species exhibit a strong origin band and several weak vibronic bands corresponding to La-ligand stretch and ligand-based bend excitations. La(C₅H₈) is a five-membered metallacycle, whereas La(C₂H₂) and La(C₃H₄) are three-membered rings. All three metallacycles prefer a doublet ground state with a La 6s¹-based valence electron configuration and a singlet ion. The five-membered metallacycle is formed through La addition and isoprene isomerization, whereas the two three-membered rings are produced by La addition and insertion, hydrogen migration, and carbon-carbon bond cleavage.

Original language	English
Article number	194302
Journal	Journal of Chemical Physics
Volume	148
Issue number	19
DOIs	https://doi.org/10.1063/1.5026899
State	Published - May 21 2018

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 No. CHE-1362102). We also acknowledge additional support from the Kentucky Science and Engineering Foundation.

Publisher Copyright:
© 2018 Author(s).

ASJC Scopus subject areas

Physics and Astronomy (all)
Physical and Theoretical Chemistry

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title = "Spectroscopy and formation of lanthanum-hydrocarbon radicals formed by association and carbon-carbon bond cleavage of isoprene",

abstract = "La atom reaction with isoprene is carried out in a laser-vaporization molecular beam source. The reaction yields an adduct as the major product and C - C cleaved and dehydrogenated species as the minor ones. La(C5H8), La(C2H2), and La(C3H4) are characterized with mass-analyzed threshold ionization (MATI) spectroscopy and quantum chemical computations. The MATI spectra of all three species exhibit a strong origin band and several weak vibronic bands corresponding to La-ligand stretch and ligand-based bend excitations. La(C5H8) is a five-membered metallacycle, whereas La(C2H2) and La(C3H4) are three-membered rings. All three metallacycles prefer a doublet ground state with a La 6s1-based valence electron configuration and a singlet ion. The five-membered metallacycle is formed through La addition and isoprene isomerization, whereas the two three-membered rings are produced by La addition and insertion, hydrogen migration, and carbon-carbon bond cleavage.",

author = "Wenjin Cao and Dilrukshi Hewage 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 No. CHE-1362102). We also acknowledge additional support from the Kentucky Science and Engineering Foundation. Publisher Copyright: {\textcopyright} 2018 Author(s).",

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doi = "10.1063/1.5026899",

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AU - Cao, Wenjin

AU - Hewage, Dilrukshi

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 No. CHE-1362102). We also acknowledge additional support from the Kentucky Science and Engineering Foundation. Publisher Copyright: © 2018 Author(s).

PY - 2018/5/21

Y1 - 2018/5/21

N2 - La atom reaction with isoprene is carried out in a laser-vaporization molecular beam source. The reaction yields an adduct as the major product and C - C cleaved and dehydrogenated species as the minor ones. La(C5H8), La(C2H2), and La(C3H4) are characterized with mass-analyzed threshold ionization (MATI) spectroscopy and quantum chemical computations. The MATI spectra of all three species exhibit a strong origin band and several weak vibronic bands corresponding to La-ligand stretch and ligand-based bend excitations. La(C5H8) is a five-membered metallacycle, whereas La(C2H2) and La(C3H4) are three-membered rings. All three metallacycles prefer a doublet ground state with a La 6s1-based valence electron configuration and a singlet ion. The five-membered metallacycle is formed through La addition and isoprene isomerization, whereas the two three-membered rings are produced by La addition and insertion, hydrogen migration, and carbon-carbon bond cleavage.

AB - La atom reaction with isoprene is carried out in a laser-vaporization molecular beam source. The reaction yields an adduct as the major product and C - C cleaved and dehydrogenated species as the minor ones. La(C5H8), La(C2H2), and La(C3H4) are characterized with mass-analyzed threshold ionization (MATI) spectroscopy and quantum chemical computations. The MATI spectra of all three species exhibit a strong origin band and several weak vibronic bands corresponding to La-ligand stretch and ligand-based bend excitations. La(C5H8) is a five-membered metallacycle, whereas La(C2H2) and La(C3H4) are three-membered rings. All three metallacycles prefer a doublet ground state with a La 6s1-based valence electron configuration and a singlet ion. The five-membered metallacycle is formed through La addition and isoprene isomerization, whereas the two three-membered rings are produced by La addition and insertion, hydrogen migration, and carbon-carbon bond cleavage.

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Spectroscopy and formation of lanthanum-hydrocarbon radicals formed by association and carbon-carbon bond cleavage of isoprene

Abstract

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