ic7b02856_si_001.pdf (997.92 kB)
Electrochemistry and Spectroelectrochemistry of Cobalt Porphyrins with π‑Extending and/or Highly Electron-Withdrawing Pyrrole Substituents. In Situ Electrogeneration of σ‑Bonded Complexes
journal contribution
posted on 2018-01-24, 12:53 authored by Xiangyi Ke, Ravi Kumar, Muniappan Sankar, Karl M. KadishA series
of cobalt porphyrins with π-extending or highly electron-withdrawing
β-pyrrole substituents were investigated as to their electrochemistry,
spectroscopic properties, and reactivity after electroreduction or
electroxidation in nonaqueous media. Each porphyrin, represented as
PorCo (where Por = TPP(NO2)Y2 or TPP(NO2)Y6 and Y = phenyl, phenylethynyl, Br, or CN) was
shown to undergo multiple redox reactions involving the conjugated
π-ring system or central metal ion which could exist in a Co(III),
Co(II), or Co(I) oxidation state under the application of an applied
oxidizing or reducing potential. Thermodynamic half-wave potentials
for the stepwise conversion between each oxidation state of [PorCo]n (where n ranged from +3
to −3) were measured by cyclic voltammetry and analyzed as
a function of the compound structure and properties of the electrochemical
solvent. UV–visible spectra were obtained for each oxidized
or reduced porphyrin in up to six different oxidation states ranging
from [PorCo]3– to [PorCo]3+ and analyzed
as a function of the compound structure and utilized electrochemical
solvent. Chemically or electrochemically generated Co(I) porphyrins
are known to be highly reactive in solutions containing alkyl or aryl
halides, and this property was utilized to in situ generate a new
series of methyl carbon-bonded cobalt(III) porphyrins with the same
π-extending or highly electron-withdrawing substituents as the
initial Co(II) derivatives. The electrosynthesized carbon-bonded Co(III)
porphyrins were then characterized as to their own electrochemical
and spectroscopic properties after the addition of one, two, or three
electrons in nonaqueous media.