Solitaire-Porphyrazines: Synthetic, Structural, and Spectroscopic Investigation of Complexes of the Novel Binucleating Norphthalocyanine-2,3-dithiolato Ligand

Abstract

We have developed the synthesis of unsymmetrical metalloporphyrazines of the form M[pz(A:B3)], where A and B refer to two different types of peripheral functionality, and have used it to prepare new bi- and trimetallic solitaire-porphyrazines in which A represents a mono- or bimetallic moiety. The macrocyclic complexes described are based on the binucleating ligand, [M(norphthalocyanine-2,3-dithiolate)]2-, [M(norpc)]2-. This can be thought of as a metalloporphyrazine where B is a fused benzo ring; A represents two thiolates fused at the β-pyrrole positions to form a dithiolene moiety that can bind a transition-metal ion in addition to one within the macrocyclic cavity. solitaire-Porphyrazines have been synthesized by chelation of [(L-L)M‘]2+ to the [M(norpc)]2- ligand where M = “2H”, Ni, Cu, or Mn-Cl, L-L is a bis(diphosphino) or bis(diamino) group and M‘ = Ni, Pd, or Pt. Crystal structures have been obtained for 11b, where the [H2(norpc)]2- ligand coordinates the diphosphinopalladium moiety, [Pd(dppf)]2+...