TY - JOUR
T1 - Comparative study of the electrochemical and pulse-radiolytic oxidation of the complexes of nickel(II) and copper(II) containing 1,4,8,11-tetra-azacyclotetradecane
AU - Zeigerson, Esther
AU - Ginzburg, Gregory
AU - Meyerstein, Dan
AU - Kirschenbaum, Louis J.
N1 - Funding Information:
This point is under furtherstudy.We thank Mrs. Mira Freiberg for providing us with asample of /Cu(cyclam)][C10,],, and the LINAC group of theHebrew University of Jerusalem for operating and main-taining the pulse-radiolysis equipment. This work wassupported in part by a grant from the U.S.-Israel Bi-national Science Foundation (BSF), Jerusalem, and by theAlberto antl Kathleen Casali Fellowship FoundationAssociation.[!,/1:32:2 Htvxivcd, 20th August, 19791K E F E R E N C E S1611; ( b ) 1971, 10, 463.Chem. SOC., 1974, 96, 3109.Inovg. Chem., 1971, 10, 1739.97, 4238.1 1). C. Olson and J. Vasilevskis, inovg. Chewz., ( a ) 1969, 8,F. V. Lovecchio, E. S. Gore, and D. I-I. Busch, J . Amer.I). P. Rillema, J. 1;.
PY - 1980/12/1
Y1 - 1980/12/1
N2 - Electrochemical and pulse-radiolytic oxidation of [Ni(cyclam)]2+ and [Cu(cyclam)]2+ (cyclam = 1,4,8,11-tetra-azacyclotetradecane) have been studied in aqueous acidic perchlorate and sulphate media. As with other nickel macrocyclic systems, [Ni(cyclam)]2+ is oxidized to NiIII, the stability of which is enhanced by sulphate complexation. In contrast, [Cu(cyclam)]3+ is much less stable than the nickel analogue and does not form a stable sulphate complex. Electrochemical oxidation of [Cu(cyclam)]2+ at pH 1.6 is a multistep process which is catalysed by sulphate ion. The mechanism appears to involve the transfer of four electrons resulting in a copper(II) macrocyclic diene complex.
AB - Electrochemical and pulse-radiolytic oxidation of [Ni(cyclam)]2+ and [Cu(cyclam)]2+ (cyclam = 1,4,8,11-tetra-azacyclotetradecane) have been studied in aqueous acidic perchlorate and sulphate media. As with other nickel macrocyclic systems, [Ni(cyclam)]2+ is oxidized to NiIII, the stability of which is enhanced by sulphate complexation. In contrast, [Cu(cyclam)]3+ is much less stable than the nickel analogue and does not form a stable sulphate complex. Electrochemical oxidation of [Cu(cyclam)]2+ at pH 1.6 is a multistep process which is catalysed by sulphate ion. The mechanism appears to involve the transfer of four electrons resulting in a copper(II) macrocyclic diene complex.
UR - http://www.scopus.com/inward/record.url?scp=37049098517&partnerID=8YFLogxK
U2 - 10.1039/DT9800001243
DO - 10.1039/DT9800001243
M3 - Article
AN - SCOPUS:37049098517
SN - 1472-7773
SP - 1243
EP - 1247
JO - Journal of the Chemical Society. Dalton Transactions
JF - Journal of the Chemical Society. Dalton Transactions
IS - 7
ER -