TY - JOUR
T1 - Photoinduced radical chain reactions between alkylcobalt(III) complexes and iodine
AU - Ishikawa, Kunio
AU - Fukuzumi, Shunichi
AU - Goto, Tatsushi
AU - Tanaka, Toshio
PY - 1990
Y1 - 1990
N2 - Cobalt-carbon bonds of various alkylcobalt(III) complexes, cis-[CoR2(bipy)2]ClO4 (R = Me, Et, or PhCH2; bipy = 2,2′-bipyridine), trans-[CoMe2(L)] (L = 3,9-dimethyl-4,8-diazaundeca-3,8-diene-2,10-dione dioximate), and [CoR(Hdmg)2(py)] (R = Me or Et; Hdmg = dimethylglyoximate; py = pyridine), are readily cleaved by iodine in carbon tetrachloride to yield alkyl iodides via photoinduced radical chain reactions with large quantum yields (e.g. Φ = 7.0 × 103) under low-energy irradiation (λ 517 nm). The rate-determining step in the radical chain reactions is suggested to be electron transfer from alkylcobalt(III) complexes to iodine atoms (I.) which are produced by the photodissociation of I2, based on the formation of by-products that could arise only via electron-transfer processes as well as the kinetic comparison between alkylcobalt(III) complexes and tetra-alkyltin compounds.
AB - Cobalt-carbon bonds of various alkylcobalt(III) complexes, cis-[CoR2(bipy)2]ClO4 (R = Me, Et, or PhCH2; bipy = 2,2′-bipyridine), trans-[CoMe2(L)] (L = 3,9-dimethyl-4,8-diazaundeca-3,8-diene-2,10-dione dioximate), and [CoR(Hdmg)2(py)] (R = Me or Et; Hdmg = dimethylglyoximate; py = pyridine), are readily cleaved by iodine in carbon tetrachloride to yield alkyl iodides via photoinduced radical chain reactions with large quantum yields (e.g. Φ = 7.0 × 103) under low-energy irradiation (λ 517 nm). The rate-determining step in the radical chain reactions is suggested to be electron transfer from alkylcobalt(III) complexes to iodine atoms (I.) which are produced by the photodissociation of I2, based on the formation of by-products that could arise only via electron-transfer processes as well as the kinetic comparison between alkylcobalt(III) complexes and tetra-alkyltin compounds.
UR - http://www.scopus.com/inward/record.url?scp=37049088744&partnerID=8YFLogxK
U2 - 10.1039/DT9900000085
DO - 10.1039/DT9900000085
M3 - Article
AN - SCOPUS:37049088744
SN - 1472-7773
SP - 85
EP - 90
JO - Journal of the Chemical Society. Dalton Transactions
JF - Journal of the Chemical Society. Dalton Transactions
IS - 1
ER -