ROM polymerization-capture-release: application to the synthesis of unsymmetrical porphyrazinedithiols and peripherally metalated derivatives

Abstract

Crossover Linstead macrocyclization of a doubly norbornenyl-functionalized dimercaptomaleonitrile with dipropylmaleonitrile gave a crude mixture of porphyrazines containing the hexapropylporphyrazinedithiol magnesium complex. The mixture was subjected to ring-opening metathesis polymerization to yield the insoluble porphyrazinedithiol-functionalized polymers. Cleavage from the polymer backbone using mercury(II) acetate followed by reaction with electrophiles gave access to a range of thioporphyrazinedithiol derivatives including solitaire porphyrazines. Studies into the possible uses of hexapropyl-2,3-di-(carboxymethylthio)porphyrazine in sensing metal cations in solution are described.