Mechanochemical insertion of cobalt into porphyrinoids using Co(CO) as a cobalt source

Cobalt porphyrinoids find broad use as catalysts or electrode materials. Traditional solution state cobalt insertion reactions into a free base porphyrinoid to generate the corresponding cobalt complex generally require fairly harsh conditions, involving the heating of the reactants in high-boiling solvents for extended period of times. We report here an alternative method of cobalt insertion: A solvent-free (at least for the insertion step) mechanochemical method using a planetary ball mill with Co 2 (CO) 8 as a cobalt source. The scope and limits of the reaction were investigated with respect to the porphyrinic substrate susceptible to the reaction conditions, the influences of different grinding aids, and bases added. While the mechanochemical method is, like other metal insertion methods into porphyrinoids, not universally suitable for all substrates tested, it is faster, milder, and greener for several others, when compared to established solution-based methods. The scopes and limits of a solvent-free mechanochemical method to prepare a range of cobalt porphyrinoids is described.