Corroles with group 15 metal ions. Synthesis and characterization of octaethylcorroles containing As, Sb, and Bi ions in +3, +4, and +5 oxidation states
Km. Kadish et al., Corroles with group 15 metal ions. Synthesis and characterization of octaethylcorroles containing As, Sb, and Bi ions in +3, +4, and +5 oxidation states, INORG CHEM, 39(15), 2000, pp. 3312-3319
The synthesis, spectroscopic characterization, and electrochemistry of As,
Sb, and Bi corroles are reported. The investigated complexes are represente
d by [(OEC)As-V(CH3)]+ClO4- and (OEC)M where M = As(III), Sb(III), or Bi(II
I) and OEC is the trianion of octaethylcorrole. The products of each redox
reaction are characterized by W-vis and ESR spectroscopy. The first one-ele
ctron oxidations of (OEC)As and (OEC)Sb are metal-centered and result in th
e formation of [(OEC)As-IV](+) and [(OEC)Sb-IV](+). A second one-electron o
xidations generates [(OEC)-As-V](2+) and [(OEC.)S-b(IV)](2+), the latter of
which is slowly converted to a Sb(V) corrole, [(OEC)Sb-V](2+). The first o
ne-electron oxidation of (OEC)Bi leads only to the Bi(III) pi-cation radica
l, but a second one-electron oxidation is proposed to give a Bi(IV) complex
, [(OEC)Bi](2+). The first reduction of [(OEC)As-V(CH3)]+ClO4- is accompani
ed by loss of the sigma-bonded methyl ligand and formation of an As(III) co
mplex.