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The chemical behavior of Fe(III) and M(III) tetraarylporphorin (TAP) complexes with N-alkylimidazoles and other suitable ligands was studied by direct reaction in the fast-atom bombardment matrix and in the gas phase. The coordination reaction occurs at the metal center and yields molecular adducts of porphyry/ligand (PL) and PL, stoichiometry. Coordinative competition between free and covalently linked ligands can be used to probe the conformation of "tailed" Mn(III)-TAP.

Fast-atom bombardment mass spectrometry has been used to investigate the chemical behavior of Fe(III) and Mn(III) tetraarylporphyrins (TAP) in both the condensed and gas phases and to clarify the mechanisms responsible for the production of positive and negative ions. The differences in the behavior of Fe(III) and Mn(III) complexes in the positive ion mode could be correlated with those in their electronic structures and knowledge of the mechanism for the generation of negatively charged species was applied to characterize the counterion coordinated to the Mn(III)-TAP. Thus, the unprecedented, complete characterization of even complex Mn(III)-TAP was made possible.