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Gas-phase reactivity of rare earth cations with phenol: Competitive activation of C-O, O-H, and C-H bonds

1998; American Chemical Society; Volume: 9; Issue: 10 Linguagem: Inglês

10.1016/s1044-0305(98)00072-5

1879-1123

José M. Carretas, António Pires de Matos, Joaquim Marçalo, M. Pissavini, Michèle Decouzon, Serge Géribaldi,

Chemical Reaction Mechanisms

The gas-phase reactions of Sc+, Y+, and Ln+ (Ln=La-Lu, except Pm) ions with phenol were studied by Fourier transform ion cyclotron resonance mass spectrometry. All the ions except Yb+ were observed to react with the organic substrate, activating O-H, C-O, and/or C-H bonds, with formation of MO+, MOH+, and/or MOC6H4+ ions as primary products. The product distributions and the reaction efficiencies obtained showed the existence of important differences in the relative reactivity of the rare earth metal cations, which are discussed in terms of factors like the electron configurations of the metal ions, their oxophilicity, and the second ionization energies of the metals. The primary product ions participated in subsequent reactions, yielding species such as M(OH)(OC6H5)+, which lead mainly to M(OC6H5)2(HOC6H5)n+ ions, where n=0–2. Formation of M(OC6H5)(HOC6H5)n+ species was also observed in the case of the metals that have high stabilities of the formal oxidation state 2+, Sm and Eu.