Spectroscopic Characterization of Lanthanum-Mediated Dehydrogenation and C-C Bond Coupling of Ethylene.
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| Abstract | :  La(C2H2) and La(C4H6) are observed from the reaction of laser-vaporized La atoms with ethylene molecules by photoionization time-of-flight mass spectrometry and characterized by mass-analyzed threshold ionization spectroscopy. La(C2H2) is identified as a metallacyclopropene and La(C4H6) as a metallacyclopentene. The three-membered ring is formed by concerted H2 elimination and the five-membered cycle by dehydrogenation and C-C bond coupling. Both metallacycles prefer a doublet ground state with a La 6s-based unpaired electron. Ionization of the neutral doublet state of either complex produces a singlet ion state by removing the La-based electron. The 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. Although the La atom is in a formal oxidation state of +2, the ionization energies of these metal-hydrocarbon cycles are lower than that of the neutral La atom. Deuteration has a small effect on the ionization energies of the two cyclic radicals but distinctive effects on their vibrational frequencies. | 
| Year of Publication | :  2016 | 
| Journal | :  The journal of physical chemistry. A | 
| Volume | :  120 | 
| Issue | :  26 | 
| Number of Pages | :  4482-9 | 
| Date Published | :  2016 | 
| ISSN Number | :  1089-5639 | 
| URL | :  https://doi.org/10.1021/acs.jpca.6b04619 | 
| DOI | :  10.1021/acs.jpca.6b04619 | 
| Short Title | :  J Phys Chem A | 
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