Spectroscopic Characterization of Nonconcerted [4 + 2] Cycloaddition of 1,3-Butadiene with Lanthanacyclopropene to Form Lanthanum-Benzene in the Gas Phase

Dilrukshi Hewage; Wenjin Cao; Jong Hyun Kim; Ya Wang; Yang Liu; Dong Sheng Yang

doi:10.1021/acs.jpca.6b12239

Spectroscopic Characterization of Nonconcerted [4 + 2] Cycloaddition of 1,3-Butadiene with Lanthanacyclopropene to Form Lanthanum-Benzene in the Gas Phase

Dilrukshi Hewage, Wenjin Cao, Jong Hyun Kim, Ya Wang, Yang Liu, Dong Sheng Yang

Chemistry

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

11 Scopus citations

Abstract

The reaction between La atoms and 1,3-butadiene is carried out in a laser-vaporization molecular beam source. Metal-hydrocarbon species with formulas La(C_nH_n) (n = 2, 4, and 6) and La(C_mH_m+2) (m = 4 and 6) are observed with time-of-flight mass spectrometry and characterized with mass-analyzed threshold ionization spectroscopy. A lanthanum-benzene complex [La(C₆H₆)] is formed by 1,3-butadiene addition to lanthanacyclopropene [La(C₂H₂)] followed by molecular hydrogen elimination. Lanthanacyclopropene is an intermediate generated by the primary reaction between La and 1,3-butadiene. Two other intermediates produced by the La + 1,3-butadiene reaction are La[η⁴-(1-buten-3-yne)] [La(C₄H₄)] and 1-lanthanacyclopent-3-ene [La(C₄H₆)]. The La(benzene) complex exhibits distinctive metal-ligand bonding from that of the three intermediates as shown by the adiabatic ionization energies and ground electron configurations.

Original language	English
Pages (from-to)	1233-1239
Number of pages	7
Journal	Journal of Physical Chemistry A
Volume	121
Issue number	6
DOIs	https://doi.org/10.1021/acs.jpca.6b12239
State	Published - Feb 16 2017

Bibliographical note

Funding Information:
This work is supported by the National Science Foundation Division of Chemistry (Chemical Structure, Dynamics, and Mechanisms Grant CHE-1362102 to D.S.Y.), the Kentucky Science and Engineering Foundation (D.S.Y.), the Natural Science Foundation of Heilongjiang province of China (Grant B2016004 to Y.L.), the Fundamental Research Funds for the Central Universities of China (Grant HIT.NSRIF.2017033 to Y.L.), and the National Natural Science Foundation of China (Grant 21203041 to Y.L)

Publisher Copyright:
© 2017 American Chemical Society.

Copyright:
Copyright 2017 Elsevier B.V., All rights reserved.

ASJC Scopus subject areas

Physical and Theoretical Chemistry

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10.1021/acs.jpca.6b12239

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@article{fd67e28c765f45d19aa60d08e653634e,

title = "Spectroscopic Characterization of Nonconcerted [4 + 2] Cycloaddition of 1,3-Butadiene with Lanthanacyclopropene to Form Lanthanum-Benzene in the Gas Phase",

abstract = "The reaction between La atoms and 1,3-butadiene is carried out in a laser-vaporization molecular beam source. Metal-hydrocarbon species with formulas La(CnHn) (n = 2, 4, and 6) and La(CmHm+2) (m = 4 and 6) are observed with time-of-flight mass spectrometry and characterized with mass-analyzed threshold ionization spectroscopy. A lanthanum-benzene complex [La(C6H6)] is formed by 1,3-butadiene addition to lanthanacyclopropene [La(C2H2)] followed by molecular hydrogen elimination. Lanthanacyclopropene is an intermediate generated by the primary reaction between La and 1,3-butadiene. Two other intermediates produced by the La + 1,3-butadiene reaction are La[η4-(1-buten-3-yne)] [La(C4H4)] and 1-lanthanacyclopent-3-ene [La(C4H6)]. The La(benzene) complex exhibits distinctive metal-ligand bonding from that of the three intermediates as shown by the adiabatic ionization energies and ground electron configurations.",

author = "Dilrukshi Hewage and Wenjin Cao and Kim, {Jong Hyun} and Ya Wang and Yang Liu and Yang, {Dong Sheng}",

note = "Funding Information: This work is supported by the National Science Foundation Division of Chemistry (Chemical Structure, Dynamics, and Mechanisms Grant CHE-1362102 to D.S.Y.), the Kentucky Science and Engineering Foundation (D.S.Y.), the Natural Science Foundation of Heilongjiang province of China (Grant B2016004 to Y.L.), the Fundamental Research Funds for the Central Universities of China (Grant HIT.NSRIF.2017033 to Y.L.), and the National Natural Science Foundation of China (Grant 21203041 to Y.L) Publisher Copyright: {\textcopyright} 2017 American Chemical Society. Copyright: Copyright 2017 Elsevier B.V., All rights reserved.",

year = "2017",

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doi = "10.1021/acs.jpca.6b12239",

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AU - Hewage, Dilrukshi

AU - Cao, Wenjin

AU - Kim, Jong Hyun

AU - Wang, Ya

AU - Liu, Yang

AU - Yang, Dong Sheng

N1 - Funding Information: This work is supported by the National Science Foundation Division of Chemistry (Chemical Structure, Dynamics, and Mechanisms Grant CHE-1362102 to D.S.Y.), the Kentucky Science and Engineering Foundation (D.S.Y.), the Natural Science Foundation of Heilongjiang province of China (Grant B2016004 to Y.L.), the Fundamental Research Funds for the Central Universities of China (Grant HIT.NSRIF.2017033 to Y.L.), and the National Natural Science Foundation of China (Grant 21203041 to Y.L) Publisher Copyright: © 2017 American Chemical Society. Copyright: Copyright 2017 Elsevier B.V., All rights reserved.

PY - 2017/2/16

Y1 - 2017/2/16

N2 - The reaction between La atoms and 1,3-butadiene is carried out in a laser-vaporization molecular beam source. Metal-hydrocarbon species with formulas La(CnHn) (n = 2, 4, and 6) and La(CmHm+2) (m = 4 and 6) are observed with time-of-flight mass spectrometry and characterized with mass-analyzed threshold ionization spectroscopy. A lanthanum-benzene complex [La(C6H6)] is formed by 1,3-butadiene addition to lanthanacyclopropene [La(C2H2)] followed by molecular hydrogen elimination. Lanthanacyclopropene is an intermediate generated by the primary reaction between La and 1,3-butadiene. Two other intermediates produced by the La + 1,3-butadiene reaction are La[η4-(1-buten-3-yne)] [La(C4H4)] and 1-lanthanacyclopent-3-ene [La(C4H6)]. The La(benzene) complex exhibits distinctive metal-ligand bonding from that of the three intermediates as shown by the adiabatic ionization energies and ground electron configurations.

AB - The reaction between La atoms and 1,3-butadiene is carried out in a laser-vaporization molecular beam source. Metal-hydrocarbon species with formulas La(CnHn) (n = 2, 4, and 6) and La(CmHm+2) (m = 4 and 6) are observed with time-of-flight mass spectrometry and characterized with mass-analyzed threshold ionization spectroscopy. A lanthanum-benzene complex [La(C6H6)] is formed by 1,3-butadiene addition to lanthanacyclopropene [La(C2H2)] followed by molecular hydrogen elimination. Lanthanacyclopropene is an intermediate generated by the primary reaction between La and 1,3-butadiene. Two other intermediates produced by the La + 1,3-butadiene reaction are La[η4-(1-buten-3-yne)] [La(C4H4)] and 1-lanthanacyclopent-3-ene [La(C4H6)]. The La(benzene) complex exhibits distinctive metal-ligand bonding from that of the three intermediates as shown by the adiabatic ionization energies and ground electron configurations.

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Spectroscopic Characterization of Nonconcerted [4 + 2] Cycloaddition of 1,3-Butadiene with Lanthanacyclopropene to Form Lanthanum-Benzene in the Gas Phase

Abstract

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