A simple method has been developed for metalation of porphyrinic compounds under homogeneous conditions at room temperature using a stable ethereal solution of MgI(2) and N,N-diisopropylethylamine. A previously developed heterogeneous procedure employs a mixture of a magnesium halide and a nonnucleophilic amine in a noncoordinating solvent at room temperature. The scope of the heterogeneous and homogeneous magnesium insertion procedures has been investigated across a family of 19 porphyrinic compounds, including synthetic porphyrins, synthetic or naturally occurring chlorins, and organic-soluble phthalocyanines. The rate of magnesium insertion increased in the series phthalocyanines < chlorins < porphyrins, which parallels the basicity of the ligands. Though phthalocyanines have the smallest core size, the magnesium phthalocyanines were far more stable than magnesium porphyrins to acid-induced demetalation. The heterogeneous method is broadly applicable to porphyrins, chlorins, and phthalocyanines. The homogeneous method is generally slower than the heterogeneous method, though both afford rapid metalation of most porphyrins, including electron-deficient, peripherally coordinating, or facially encumbered meso-substituted tetraarylporphyrins, and the beta-substituted octaethylporphyrin. Chlorin e(6) trimethyl ester and methyl pyropheophorbide a were metalated cleanly under homogeneous but not heterogeneous conditions, while pheophytin a failed with both methods. The homogeneous method failed altogether with phthalocyanines. Several methods in magnesium chemistry have been developed that augment these procedures, including a mild synthesis of tetraphenylchlorin and a streamlined separation of porphyrin, chlorin, and bacteriochlorins based on selective formation of the magnesium chelates. Collectively, these methods should broaden the scope of model systems based on magnesium chelates of porphyrinic compounds.
