Three Oxidation States of Cobalt(I/II/III) Complexes by Thiaporphyrin.

Reaction of tetraphenyl-21-thiaporphyrin (HSTPP) with cobalt salt yields a pentacoordinated high-spin 3/2 [CoCl(STTP)] (). Through ion exchange, a roughly square-planar-geometry low-spin 1/2 CoSTTP(BArF) () 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.