Redox Chemistry of Tetrakis[5,6‐di(2‐pyridyl)‐2,3‐pyrazino]porphyrazinatocobalt(II): Isolation and Characterization of Solid Pure CoI, CoII, and CoIII Complexes

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Salt‐like hydrated complexes of formulae Na[Py8TPyzPzCo] and [Py8TPyzPzCo](SbCl6) containing CoI and CoIII, respectively, and the neutral CoII–bis(dimethyl sulfoxide) (DMSO) adduct [Py8TPyzPzCo(DMSO)2], bearing additional clathrated DMSO molecules, have been prepared and characterized {Py8TPyzPz = tetrakis[5,6‐di(2‐pyridyl)‐2,3‐pyrazino]porphyrazinato dianion}. The sodium CoI salt, the anion of which, [Py8TPyzPzCo]1–, had previously been identified by electrochemical solution studies, represents the first example of a CoI derivative of a tetrapyrrolic macrocyclic chromophore prepared as a solid pure material. Solutions of Na[Py8TPyzPzCo] in DMSO, under defined experimental conditions, allow the slow formation (months) of crystals of its corresponding CoII complex of formula [Py8TPyzPzCo(DMSO)2]·6 DMSO. The structure of the adduct, elucidated by single‐crystal X‐ray analysis, shows the central CoII ion surrounded by the four pyrrole N atoms of the porphyrazine macrocycle and two O atoms of the axially bonded DMSO molecules. Oxidation of the basic starting material [Py8TPyzPzCo] with phenoxathiin hexachloroantimonate (phenox‐SbCl6) led to the formation of the CoIII complex [Py8TPyzPzCo](SbCl6). Full characterization of the title CoI, CoII, and CoIII species has been accomplished by solution studies and from IR, UV/Vis, EPR and X‐ray crystallography data.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)