C(2)-H isotopic exchange in coordinated imidazoles revisited.: The case of the [Co(NH3)5ImH]3+ ion

被引：0
|
作者：
Clark, CR [1 ]
Blackman, AG [1 ]
Grimmett, MR [1 ]
Mobinikhaledi, A [1 ]
机构：
[1] Univ Otago, Dept Chem, Dunedin, New Zealand
来源：
CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE | 1999年 / 77卷 / 02期
关键词：
kinetics; H/D-exchange; imidazole; metal complex;
D O I：
暂无
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
The temperature dependence of the acid ionization constants of [Co(NH3)(5)ImH](3+) in H2O (I = 1.0 M (NaClO4)): pK(a) (degrees C)= 10.10 +/- 0.04 (25.0), 9.92 +/- 0.03 (30.0), 9.82 +/- 0.02 (35.0), 9.62 +/- 0.03 (40.0), and [Co(ND3)(5)ImD](3+) in D2O (I = 0.35 M (NaClO4)): pK(a) (degrees C) = 10.58 +/- 0.06 (25.0), 9.46 +/- 0.08 (60.0) is reported. Observed first-order rate constants for H/D exchange at C-2 in [Co(ND3)(5)ImD](3+) over the pD range 8.08-11.20 (60.0 degrees C, I = 0.35 M (NaClO4)) follow an equation of the form: k(obs) = k(OD)K(w)/(a(D+) + K-a)gamma(+/-), with k(OD) (0.27 +/- 0.06 M-1 s(-1)) corresponding to the rate constant for OD--catalyzed abstraction of H-2 in [Co(ND3)(5)ImD](3+) and K-a ((2.8 +/- 0.7) x 10(-10) M, pK(a) = 9.55 +/- 0.13) to the acid ionization constant of this species. No evidence was found for a pathway to H/D exchange in the imidazolate moiety of [Co(ND3)(5)Im](2+).
引用
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页码：178 / 181
页数：4
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