TY - JOUR
T1 - Complexes of zinc(I), cadmium(I), and mercury(I) with 1, 4, 8, 11-tetraazacyclotetradecane in aqueous solutions A pulse radiolytic study
AU - Weddell, James K.
AU - Allred, A. Louis
AU - Meyerstein, Dan
AU - Mulac, William A.
N1 - Funding Information:
Reagent grade materials were used without further purification in the syntheses of the metal complexes. The complexes were prepared by published procedures \[3\] except that the final precipitation was carried out from a minimum amount of acetonitrile with cooling and addition of ether. Solutions for pulse radiolysis studies were prepared from triply distilled water and, when necessary, analytical grade tert-butyl alcohol (J. T. Baker) to scavenge hydroxyl radicals. The pH of all solutions was between 5 and 7. The techniques for saturating with gases and for filling cells have been described previously \[4\]. Spectra of the transient species produced by single electron pulses were obtained using a streak camera--TV scanning method described in a previous publication\[5\]. The procedures for irradiation and measurement of dosage are explained elsewhere \[6\].F or the streak camera experiments 0.25-3/~s pulses of +Work performed in part under the auspices of the Division of Basic Energy Sciences of the U.S. Department of Energy. This research was partially supported by the National Science Foundation (Grant No. CHE 76-10328). :~Visiting scientist from the Nuclear Research Center Negev and the Ben-Guelph University ofNegev, Beer-Sheva, Israel.
PY - 1980
Y1 - 1980
N2 - The absorption spectra of 1,4,8, 11-tetraazacyclotetradecane (L or cyclam) complexes of Zn(I), Cd(I), and Hg(I) and of the products resulting from the OH reaction with the M(II)L complexes in water were observed. The values of λmax were 330±10 nm for Zn(I)L and 340±10 Nm for Cd(I)L. Second-order rate constants (M-1s-1) were measured for the following reactions: Zn(II)L + eaq-, (7.2 ± 0.7) × 108; Cd(II)L + eaq-, (2.8 ± 0.3) × 1010; Hg(II) + eaq-, (4.2 ± 0.4) × 1010; M(II)L + OH, (7 ± 2) × 109; Zn(I)L + N2O, (6.4 ± 1.3) × 107; Cd(I)L + N2O, (4.5 ± 0.9) × 107. Zn(I)L and Cd(I)L react more rapidly with N2O than do the corresponding aquo species. A relatively long-lived (t 1 2 ≅ 0.04 sec) mercury(I) complex (λmax = 328 ± 2 nm) was formed following reactions of Hg(II)L with eaq- or with OH.
AB - The absorption spectra of 1,4,8, 11-tetraazacyclotetradecane (L or cyclam) complexes of Zn(I), Cd(I), and Hg(I) and of the products resulting from the OH reaction with the M(II)L complexes in water were observed. The values of λmax were 330±10 nm for Zn(I)L and 340±10 Nm for Cd(I)L. Second-order rate constants (M-1s-1) were measured for the following reactions: Zn(II)L + eaq-, (7.2 ± 0.7) × 108; Cd(II)L + eaq-, (2.8 ± 0.3) × 1010; Hg(II) + eaq-, (4.2 ± 0.4) × 1010; M(II)L + OH, (7 ± 2) × 109; Zn(I)L + N2O, (6.4 ± 1.3) × 107; Cd(I)L + N2O, (4.5 ± 0.9) × 107. Zn(I)L and Cd(I)L react more rapidly with N2O than do the corresponding aquo species. A relatively long-lived (t 1 2 ≅ 0.04 sec) mercury(I) complex (λmax = 328 ± 2 nm) was formed following reactions of Hg(II)L with eaq- or with OH.
UR - http://www.scopus.com/inward/record.url?scp=0345101282&partnerID=8YFLogxK
U2 - 10.1016/0022-1902(80)80243-0
DO - 10.1016/0022-1902(80)80243-0
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AN - SCOPUS:0345101282
SN - 0022-1902
VL - 42
SP - 219
EP - 222
JO - Journal of Inorganic and Nuclear Chemistry
JF - Journal of Inorganic and Nuclear Chemistry
IS - 2
ER -