Mass-analyzed threshold ionization spectroscopy of lanthanum-hydrocarbon radicals formed by C - H bond activation of propene

Sudesh Kumari, Wenjin Cao, Dilrukshi Hewage, Ruchira Silva, Dong Sheng Yang

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Abstract

La(C3H4) and La(C3H6) are observed from the reaction of laser-vaporized La atoms with propene by photoionization time-of-flight mass spectrometry and characterized by mass-analyzed threshold ionization spectroscopy. Two isomers of La(C3H4) are identified as methyl-lanthanacyclopropene [La(CHCCH3)] (Cs) and lanthanacyclobutene [La(CHCHCH2)] (C1); La(C3H6) is determined to be H - La(η3-allyl) (Cs), a C - H bond inserted species. All three metal-hydrocarbon radicals prefer a doublet ground state with a La 6s-based electron configuration. Ionization of the neutral doublet state of each of these radicals produces a singlet ion state by removing the La-based 6s electron. The threshold ionization allows accurate measurements of the adiabatic ionization energy of the neutral doublet state and metal-ligand and ligand-based vibrational frequencies of the neutral and ionic states. The formation of the three radicals is investigated by density functional theory computations. The inserted species is formed by La inserting into an allylic C - H bond and lanthanacyclopropene by concerted vinylic H2 elimination, whereas lanthanacyclobutene involves both allylic and vinylic dehydrogenations. The inserted species is identified as an intermediate for the formation of lanthanacyclobutene.

Original languageEnglish (US)
Article number074305
JournalJournal of Chemical Physics
Volume146
Issue number7
DOIs
StatePublished - Feb 21 2017

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. S.K. thanks Tao Hong Li for the help in reaction pathway calculations.

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