Abstract
Nascent laser-ablated lanthanide metal ions, Ln+, were reacted with cyclohexacarbons, C6H6+2n (n = 0, 1, 2, or 3), and the resulting organometallic complex ions, {Ln+}−{CpHq}, were identified by time-of-flight mass spectrometry. Cyclohexane and cyclohexadiene were especially reactive, primarily undergoing one or more dehydrogenations to produce adduct ions corresponding to the benzene and benzyne complexes, {Ln+}−{C6H6} and {Ln+}−{C6H4}. Also identified as minor products were the “sandwich” complexes, {C6H6}−{Ln+}−{C6H6}. Carbon−carbon bond activation was generally an unimportant reaction channel, with small yields of {Ln+}−{CpHq} for p ≤ 5. Significant differences were observed in product yields and distributions between the several Ln+ studied, providing the following comparative reactivities: Ce+ ≳ Tb+ ≳ Gd+ ≈ Pr+ ≳ Ho+ ≳ Dy+ ≳ Lu+ > [Sm+/Tm+/Eu+/Yb+ unreactive]. These differences are explained by the metal ion ground state electronic configurations (typically 4fn-1 6s1) and promotion energies (PE) fo...
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