TY - JOUR
T1 - Cleavage of Cobalt-Alkyl Bonds of N-Dialkyleobalt (III) Complexes with Organic Oxidants Catalyzed by Mg(CIO4)2 and HCIO4
AU - Fukuzumi, Shunichi
AU - Ishikawa, Kunio
AU - Tanaka, Toshio
PY - 1985
Y1 - 1985
N2 - Electron transfer from crs-dialkylcobalt (III) complexes, cis-[R2Co(bpy)2]C1O4 (R=Me, Et; bpy=2, 2'-bipyridine), to strong organic oxidants (2, 3-dichloro-5, 6-dicyano-p-benzoquinone, 2, 3-dieyano-p-benzoquinone, tetracyanoethylene, and 7, 7, 8, 8-tetraeyano-p-quinodimethan) in aeetonitrile results in the cleavage of a pair of the cobalt-alkyl bonds to yield the coupled products (R-R) exclusively. The cleavage of the cobalt-alkyl bonds of cis-[R2Co(bpy)2]+ with weaker organic oxidants such as p-benzoquinone was catalyzed significantly by Mg(C1O4)2 and HC1O4. The presence of both Mg(C1O4)2 and HC1O4 showed a much larger catalytic effect than that of Mg(C1O4)2 or HC1O4 alone. It has been studied a correlation of the logarithm of rate constants with the difference of the redox potentials between cis-[R2Co(bpy)2]+ and the oxidants in the absence and presence of Mg(C1O4)2, and presence of both Mg(C1O4)2 and HC1O4. Then, the role of Mg(C1O4)2 and HC1O4 in the cleavage of the cobalt-alkyl bonds of cis-[R2Co(bpy)2]+ with p-benzoquinone derivatives was found to be due to the increased electron-accepting property of the oxidants, resulting in the acceleration of electron transfer from cis-[R2Co(bpy)2]+ to the oxidants.
AB - Electron transfer from crs-dialkylcobalt (III) complexes, cis-[R2Co(bpy)2]C1O4 (R=Me, Et; bpy=2, 2'-bipyridine), to strong organic oxidants (2, 3-dichloro-5, 6-dicyano-p-benzoquinone, 2, 3-dieyano-p-benzoquinone, tetracyanoethylene, and 7, 7, 8, 8-tetraeyano-p-quinodimethan) in aeetonitrile results in the cleavage of a pair of the cobalt-alkyl bonds to yield the coupled products (R-R) exclusively. The cleavage of the cobalt-alkyl bonds of cis-[R2Co(bpy)2]+ with weaker organic oxidants such as p-benzoquinone was catalyzed significantly by Mg(C1O4)2 and HC1O4. The presence of both Mg(C1O4)2 and HC1O4 showed a much larger catalytic effect than that of Mg(C1O4)2 or HC1O4 alone. It has been studied a correlation of the logarithm of rate constants with the difference of the redox potentials between cis-[R2Co(bpy)2]+ and the oxidants in the absence and presence of Mg(C1O4)2, and presence of both Mg(C1O4)2 and HC1O4. Then, the role of Mg(C1O4)2 and HC1O4 in the cleavage of the cobalt-alkyl bonds of cis-[R2Co(bpy)2]+ with p-benzoquinone derivatives was found to be due to the increased electron-accepting property of the oxidants, resulting in the acceleration of electron transfer from cis-[R2Co(bpy)2]+ to the oxidants.
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U2 - 10.1246/nikkashi.1985.62
DO - 10.1246/nikkashi.1985.62
M3 - Article
AN - SCOPUS:84917871283
SN - 0369-4577
VL - 1985
SP - 62
EP - 69
JO - NIPPON KAGAKU KAISHI
JF - NIPPON KAGAKU KAISHI
IS - 1
ER -