期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 137, 期 3, 页码 1322-1329出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja512014z
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资金
- NIH [GM47365]
- NSF-MRI [CHE-1229400]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1229400] Funding Source: National Science Foundation
With the aim of understanding the basis for the high rate of hydrogen atom abstraction (HAT) from dihydroanthracene (DHA) by the complex LCuOH (1; L = N,N'-bis(2,6-diisopropylphenyl)-2,6-pyridinedicarboxamide), the bond dissociation enthalpy of the reaction product LCu(H2O) (2) was determined through measurement of its pKa and E1/2 in THF solution. In so doing, an equilibrium between 2 and LCu(THF) was characterized by UV-vis and EPR spectroscopy and cyclic voltammetry (CV). A high pKa of 18.8 +/- 1.8 and a low E1/2 of -0.074 V vs Fc/Fc+ in THF combined to yield an O-H BDE for 2 of 90 +/- 3 kcal mol(-1) that is large relative to values for most transition metal oxo/hydroxo complexes. By taking advantage of the increased stability of 1 observed in 1,2-difluorobenzene (DFB) solvent, the kinetics of the reactions of 1 with a range of substrates with varying BDE values for their C-H bonds were measured. The oxidizing power of 1 was revealed through the accelerated decay of 1 in the presence of the substrates, including THF (BDE = 92 kcal mol(-1)) and cyclohexane (BDE = 99 kcal mol(-1)). CV experiments in THF solvent showed that 1 reacted with THF via rate-determining attack at the THF C-H(D) bonds with a kinetic isotope effect of 10.2. Analysis of the kinetic and thermodynamic data provides new insights into the basis for the high reactivity of 1 and the possible involvement of species like 1 in oxidation catalysis.
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