TY - JOUR
T1 - Lanthanum-mediated dehydrogenation of 1- and 2-butynes
T2 - Spectroscopy and formation of La(C4H4) isomers
AU - Cao, Wenjin
AU - Hewage, Dilrukshi
AU - Yang, Dong Sheng
N1 - Publisher Copyright:
© 2017 Author(s).
PY - 2017/8/14
Y1 - 2017/8/14
N2 - La atom reactions with 1-butyne and 2-butyne are carried out in a laser-vaporization molecular beam source. Both reactions yield the same La-hydrocarbon products from the dehydrogenation and carbon-carbon bond cleavage and coupling of the butynes. The dehydrogenated species La(C4H4) is characterized with mass-analyzed threshold ionization (MATI) spectroscopy and quantum chemical computations. The MATI spectra of La(C4H4) produced from the two reactions exhibit two identical transitions, each consisting of a strong origin band and several vibrational intervals. The two transitions are assigned to the ionization of two isomers: La(η4-CH2CCCH2) (Iso A) and La(η4-CH2CHCCH) (Iso B). The ground electronic states are 2A1 (C2v) for Iso A and 2A (C1) for Iso B. The ionization of the doublet state of each isomer removes a La 6s-based electron and results in a 1A1 ion of Iso A and a 1A ion of Iso B. The formation of Iso A from 2-butyne and Iso B from 1-butyne involves the addition of La to the C=C triple bond, the activation of two C(sp3)-H bonds, and concerted elimination of a H2 molecule. The formation of Iso A from 1-butyne and Iso B from 2-butyne involves the isomerization of the two butynes to 1,2-butadiene in addition to the concerted H2 elimination.
AB - La atom reactions with 1-butyne and 2-butyne are carried out in a laser-vaporization molecular beam source. Both reactions yield the same La-hydrocarbon products from the dehydrogenation and carbon-carbon bond cleavage and coupling of the butynes. The dehydrogenated species La(C4H4) is characterized with mass-analyzed threshold ionization (MATI) spectroscopy and quantum chemical computations. The MATI spectra of La(C4H4) produced from the two reactions exhibit two identical transitions, each consisting of a strong origin band and several vibrational intervals. The two transitions are assigned to the ionization of two isomers: La(η4-CH2CCCH2) (Iso A) and La(η4-CH2CHCCH) (Iso B). The ground electronic states are 2A1 (C2v) for Iso A and 2A (C1) for Iso B. The ionization of the doublet state of each isomer removes a La 6s-based electron and results in a 1A1 ion of Iso A and a 1A ion of Iso B. The formation of Iso A from 2-butyne and Iso B from 1-butyne involves the addition of La to the C=C triple bond, the activation of two C(sp3)-H bonds, and concerted elimination of a H2 molecule. The formation of Iso A from 1-butyne and Iso B from 2-butyne involves the isomerization of the two butynes to 1,2-butadiene in addition to the concerted H2 elimination.
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U2 - 10.1063/1.4997567
DO - 10.1063/1.4997567
M3 - Article
C2 - 28810759
AN - SCOPUS:85027281416
SN - 0021-9606
VL - 147
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 6
M1 - 064303
ER -