Solitaire porphyrazines

Structural Characterization. Solitaire porphyrazines (67b and 67h) have been crystallographically characterized (4). As Table XVI indicates, the Cp-Cp-S angles and S-S distances for 67b and 67h are significantly smaller and shorter than those reported for the uncoordinated. V-methyl pz 46. These smaller bond angles and shorter bond distances are attributable to the... 

As Table XVIII shows, the solitaire pzs, 66a and 67b have reductions very close to those reported for H2(pc) and are more negative than those reported for 47. Additionally, for solitaire porphyrazines 67b-67d, which have a [l,T-(diphenylphosphino) ferrocene] palladium(II) peripheral ligand, a reversible one-electron oxidation due to the ferrocene was measured at +0.18 V. 

B = molybdocene(IV) dithiol (70b). The solitaire porphyrazines exhibited rich redox chemistry, and could be oxidized with ferrocenium hexafluorophosphate to yield the paramagnetic Mo(V) species H2[pz(A3B)], A = di -ferf-butyl phenyl, B = molybdocene(V) dithiol (72a) and H2[pz(A3B)], A = dipropyl, B = molybdocene(V) dithiol (72b), which were studied by EPR (Scheme 13). Additionally, 70a was centrally metalated with Cu(II), to form Cun[pz(A3B)], A = di-ferf-butyl phenyl, B = molybdocene(IV) dithiol (71), which was then oxidized to Cun[pz(A3B)], A = di-terf-butyl phenyl, B = molybdocene(V) dithiol (73) and its magnetic properties investigated. 

The coordination of PdCl2 and PtCl2 to the single peripheral bis(dimethylamino) chelating site of the unsymmetrical porphyrazines 128 (Ni) and 129 (Cu) results in the formation of the bimetalic solitaire porphyrazines 143 (95%), 144 (72%), 145 (no yield reported), 146 (no yield reported), indicated by a color change from blue to purple and a sharpening of the g-band region (Scheme 27) (29). 

A set of truncated phthalocyanines with three isoindoline subunits cloned with a dithiolate substructure called solitaire porphyrazines have been prepared recently by the mixed condensation of phthalonitrile (in excess) with a dithiomaleonitrile... 

Scheme 13. Preparation of solitaire molybdocene porphyrazines. [Adapted from (6).]...

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