Porphyrazinediols:  Synthesis, Characterization, and Complexation to Group IVB Metallocenes

The first metalated porphyrazinediols 11 have been prepared from (l)-(+)-dimethyl tartrate via conversion into the corresponding dispoke or 2,3-dimethoxy-2,3-butanediyl protected 2,3-dihydroxymaleonitrile, Linstead macrocyclization, transmetalation, and deprotection. Their stability is very dependent on the nature of the metal ion in the cavity of the porphyrazine. Reaction of these porphyrazinediols with metallocene dichlorides led to new solitaire porphyrazines 12 while DDQ oxidation followed by trapping with diaminomaleonitrile afforded new porphyrazine dinitriles 14.