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Spectroscopy and formation of lanthanum-hydrocarbon radicals formed by C-H and C-C bond activation of 1-pentene and 2-pentene.
J Chem Phys ; 149(3): 034303, 2018 Jul 21.
Artigo em Inglês | MEDLINE | ID: mdl-30037237
ABSTRACT
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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Texto completo: Disponível Coleções: Bases de dados internacionais Base de dados: MEDLINE Idioma: Inglês Revista: J Chem Phys Ano de publicação: 2018 Tipo de documento: Artigo País de afiliação: Estados Unidos