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Spectroscopic Characterization of Nonconcerted [4 + 2] Cycloaddition of 1,3-Butadiene with Lanthanacyclopropene To Form Lanthanum-Benzene in the Gas Phase.

J Phys Chem A; 121(6): 1233-1239, 2017 Feb 16.
Artigo em Inglês | MEDLINE | ID: mdl-28124565
The reaction between La atoms and 1,3-butadiene is carried out in a laser-vaporization molecular beam source. Metal-hydrocarbon species with formulas La(C H ) (n = 2, 4, and 6) and La(C H ) (m = 4 and 6) are observed with time-of-flight mass spectrometry and characterized with mass-analyzed threshold ionization spectroscopy. A lanthanum-benzene complex [La(C H )] is formed by 1,3-butadiene addition to lanthanacyclopropene [La(C H )] followed by molecular hydrogen elimination. Lanthanacyclopropene is an intermediate generated by the primary reaction between La and 1,3-butadiene. Two other intermediates produced by the La + 1,3-butadiene reaction are La[η -(1-buten-3-yne)] [La(C H )] and 1-lanthanacyclopent-3-ene [La(C H )]. The La(benzene) complex exhibits distinctive metal-ligand bonding from that of the three intermediates as shown by the adiabatic ionization energies and ground electron configurations.