Migration Reactivities of sigma-Bonded Ligands of Organoiron and Organocobalt Porphyrins Depending on Different High Oxidation States.
Migration reactivities of sigma-bonded organo-iron and -cobalt porphyrins were examined as a function of the compound oxidation state. Migration rates were determined for both the one-electron and two-electron oxidized species produced in the electron-transfer oxidation with different oxidants in acetonitrile at 298 K. The investigated compounds are represented as [(OETPP)Fe(R)](n)()(+), where n = 1 or 2, OETPP = the dianion of 2,3,7,8,12,13,17,18-octaethyl-5,10,15,20-tetraphenylporphyrin, and R = C(6)H(5), 3,5-C(6)F(2)H(3), or C(6)F(5), and as [(TPP)Co(R)](n)()(+), where n = 1 or 2, TPP = the dianion of 5,10,15,20-tetraphenylporphyrin, and R = CH(3) or C(6)H(5). The rapid two-electron oxidation of (OETPP)Fe(III)(R) occurs with [Ru(bpy)(3)](3+) (bpy = 2,2'-bipyridine) to produce [(OETPP)Fe(IV)(R)](2+). The formation of this species is followed by a slow migration of the sigma-bonded R group to a nitrogen of the porphyrin ring to give [(N-ROETPP)Fe(II)](2+) and then by a rapid electron-transfer oxidation of the migrated product with [Ru(bpy)(3)](3+) to yield [(N-ROETPP)Fe(III)](3+) as a final product. When [Ru(bpy)(3)](3+) is replaced by a much weaker oxidant such as ferricenium ion, only the one-electron oxidation of (OETPP)Fe(R) occurs to produce [(OETPP)Fe(IV)(R)](+). A migration of the R group also occurs in the one-electron oxidized porphyrin species, [(OETPP)Fe(IV)(R)](+), to produce [(N-ROETPP)Fe(II)](+), which is rapidly oxidized by ferricenium ion to yield [(N-ROETPP)Fe(III)](2+). The migration rate of the R group in [(OETPP)Fe(IV)(R)](+) is about 10(4) times slower than the migration rate of the corresponding two-electron oxidized species, [(OETPP)Fe(IV)(R)](2+). The migration rate of the sigma-bonded ligand of [(TPP)Co(IV)(R)](+), produced by the one-electron oxidation of (TPP)Co(III)(R) with [Fe(phen)(3)](3+) (phen = 1,10-phenanthroline) is also about 10(4) times slower than the migration rate of the R group in the corresponding two-electron oxidized species, [(TPP)Co(IV)(R)](2+), which is produced by the two-electron oxidation with [Ru(bpy)(3)](3+). A comparison of the migration rates with the oxidation states of the porphyrins indicates that the migration occurs via an intramolecular electron transfer from the R group to the Fe(IV) or Co(IV) metal of the organometallic porphyrin.
Fukuzumi
Shunichi
S
Department of Material and Life Science, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan, LIMSAG, UMR 5633, Faculté des Sciences "Gabriel", Université de Bourgogne, 6 Boulevard Gabriel, 21000 Dijon, France, and Department of Chemistry, University of Houston, Houston, Texas 77204-5641.
Nakanishi
Ikuo
I
Tanaka
Keiko
K
Tabard
Alain
A
Guilard
Roger
R
Caemelbecke
Eric Van
EV
Kadish
Karl M.
KM