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Reaction of tetraphenyl-21-thiaporphyrin (HSTPP) with cobalt salt yields a pentacoordinated high-spin 3/2 CoIICl(STTP) (1). Through ion exchange, a roughly square-planar-geometry low-spin 1/2 CoIISTTP(BArF24) (2) complex was isolated. These two paramagnetic precursors were examined by single X-ray diffraction, nuclear magnetic resonance, electron paramagnetic resonance, superconducting quantum interference device, and density functional theory calculations. These two allowed the development of one electron reduction and oxidation to give CoI(STTP) (3), CoIII(STTP)Cl(CH3CN)(BF4) (4), and CoIII(STTP)Cl2 (5). The products of the chemical redox reactions were isolated and fully characterized. In addition, the reactivity of CoIICl(STTP) (1) was examined by azide (N3), cyanate (OCN), and thiocyanate (SCN) and featured a preferential N-coordination to the cobalt metal.
Wang et al. (Mon,) studied this question.