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• W2083080509 abstract "η2-Propadienylidenelanthanum [La(η2-CCCH2)] and deprotiolanthanacyclobutadiene [La(HCCCH)] of La(C3H2) are identified from the reaction mixture of neutral La atom activation of propyne in the gas phase. The two isomers are characterized with mass-analyzed threshold ionization spectroscopy combined with electronic structure calculations and spectral simulations. La(η2-CCCH2) and La(HCCCH) are formed by concerted 1,3- and 3,3-dehydrogenation, respectively. Both isomers prefer a doublet ground state with a La 6s-based unpaired electron, and La(η2-CCCH2) is slightly more stable than La(HCCCH). Ionization of the neutral doublet state of either isomer produces a singlet ion state by removing the La-based electron. The geometry change upon ionization results in the excitation of a symmetric metal–hydrocarbon stretching mode in the ionic state, whereas thermal excitation leads to the observation of the same stretching mode in the neutral state. Although the La atom is in a formal oxidation state of +2, the ionization energies of these metal–hydrocarbon radicals are lower than that of the neutral La atom. Deuteration has a very small effect on the ionization energies of the two isomers and the metal–hydrocarbon stretching mode of La(η2-CCCH2), but it reduces considerably the metal–ligand stretching frequencies of La(HCCCH)." @default.
• W2083080509 created "2016-06-24" @default.
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• W2083080509 date "2015-03-10" @default.
• W2083080509 modified "2023-10-14" @default.
• W2083080509 title "Lanthanum-Mediated C–H Bond Activation of Propyne and Identification of La(C₃H₂) Isomers" @default.
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• W2083080509 doi "https://doi.org/10.1021/jp512777e" @default.
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