engleski

Gas-phase metallation reactions of porphyrins with metal monocations

The gas-phase reactions of octaethylporphyrin (H2P, III) with twelve metal monocations, which were produced by laser ablation of Al, V, Cr, Fe, Ni, Nb, Mo, Hf, W, Re, Pt and Au targets in an ICR-FTMS instrument, revealed three possible reaction pathways: i) charge transfer ; ii) metal incorporation (ligation) with loss of H2 ; and iii) "dimerization" of the ligation product from ii) by addition of another porphyrin without further loss of H2. These differences in metal behavior are discussed. The reaction of a mixture of hexaethyldimethylporphyrin (H2P, I) and pentaethyltrimethylporphyrin (H2P, II) with neat Fe+ was also investigated ; it was found that more than half of the Fe+ reacts by charge exchange and that the lower-alkylated porphyrin (I), which has the higher ionization energy (IE), reacts more slowly in charge exchange but with the same rate in the both ligation and "dimerization" reactions as the higher alkylated porphyrin (H2P, II).

porphyrins; metal monocation

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