La atom reactions with 1-pentene and 2-pentene are carried out in a laser-vaporization molecular beam source. The two reactions yield the same metal-hydrocarbon products from the dehydrogenation and carbon–carbon bond cleavage of the pentene molecules. The dehydrogenated species La(C5H8) is the major product, whereas the carbon–carbon bond cleaved species La(C2H2) and La(C3H4) are the minor ones. La(C10H18) is also observed and is presumably formed by La(C5H8) addition to a second pentene molecule. La(C5H8) and La(C2H2) are characterized with mass-analyzed threshold ionization (MATI) spectroscopy and quantum chemical computations. The MATI spectra of each species from the two reactions exhibit the same transitions. Adiabatic ionization energies and metal-ligand stretching frequencies are determined for the two species, and additional methyl bending and torsional frequencies are measured for the larger one. Five possible isomers are considered for La(C5H8), and a C1 metallacyclopentene (Iso A) is identified as the most possible isomer. La(C2H2) is confirmed to be a C2v metallacyclopropene. The ground electronic state of each species is a doublet with a La 6s1-based electron configuration, and ionization yields a singlet state. The formation of the lanthanacyclopentene includes La addition to the C=C double bond, La insertion into two C(sp3)—H bonds, and concerted dehydrogenation. For the 2-pentene reaction, the formation of the five-membered ring may also involve 2-pentene to 1-pentene isomerization. In addition to the metal addition and insertion, the formation of the three-membered metallacycle from 1-pentene includes C(sp3)—C(sp3) bond breakage and hydrogen migration from La to C(sp3), whereas its formation from 2-pentene may involve the ligand isomerization.

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Published in The Journal of Chemical Physics, v. 149, issue 3, 034303, p. 1-9.

© 2018 Author(s)

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This article appeared in The Journal of Chemical Physics, v. 149, issue 3, 034303, p. 1-10 and may be found at https://doi.org/10.1063/1.5022771.

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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.

Related Content

See supplementary material for the geometries of the La(C5H8) and La(C2H2), the electronic energies, enthalpies, and free energies of the stationary points along the reaction coordinates for the formation of the two species, simulations of four higher-energy La(C5H8) isomers, and the reaction pathway and energy profile for the formation of La(C2H2) by the La(C5H8) decomposition.

La + pentens-supplement-JCP-rev 2.docx (608 kB)
Supplementary Material