Noble Metal Azaporphyrinates

Phthalocyanines - Pthalocyanine complexes form a very large class among tetrapyrrole complexes. Their chemistry, physics, and applications for novel materials are being reviewed in a multi volume series [106]. Usually they are made by reductive tetramerization of phthalodinitrile with a metal salt (see below), but metallations of free phthalocyanine, H2(Pc), are also documented. Work in the last two decades has been concentrated on phthalocyanine complexes of Ru, Os, Rh, Pd, Pt, and Ag Berezin gives references on IrCl(Pc) and AuCl(Pc) [107]. 

Ruthenium and Osmium Phthalocyaninates - By cyclization of phthalodinitrile with RuC13(H20)3 or Os04 in the presence of carbon monoxide or with the corresponding trimetal dodecacarbonyls, the pure complexes RuCO(Pc) Py and OsCO(Pc) Py have been obtained in good yields [108]. o-Cyanobenzamide and RuC13(H20)3 [109] produced so-called crude Ru(Pc) and, after extraction with pyridines, complexes like Ru(Pc)Py2. 

Heating OsCl3 HzO with o-cyanobenzamide in a naphthalene melt gave a product, OsL2(Pc) with unidentified axial ligands L, which was slowly heated to 400 °C in vacuo whereupon analytically pure Os(Pc) remained [113]. Extraction of the product with pyridine before sublimation yielded OsPy2(Pc) which loses two moles of pyridine on heating in vacuo to 400 °C as above [114]. 

Rhodium phthalocyaninates - Well-defined rhodium(III) phthalocyanines RhX(PcXMeOH) (X = Cl, Br, I) with halide and methanol as axial ligands were prepared for photochemical investigations [118]. 

For the insertion of noble metal ions into phthalocyanine H2(Pc), the latter is favorably activated by transformation into its lithium derivative. Thus, reaction of Li2(Pc) with [Rh(COD)Cl]2 in a large excess of a donor solvent L yielded the Rh(II) complexes, Rh(Pc) L2 (L = Py, BuNH2, Bipy, Pyz) [119]. The formation of these Rh(II) species is very remarkable because Rh insertions normally yield either Rh(I) or Rh(III) derivatives. Recently, tris(ethylenediamine)-rhodium(III) iodide [Rh(en)3]I3 and phthalodinitrile have been used to prepare H [RhI2(Pc)] 2phthalodinitrile. This material was then transformed into [Rh(OH)2(Pc)] by treatment with first H2SQ4 and then KOH. Treatment of 

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