Structural Characterization and Oxidation Reactivity of a Nickel(II) Acylperoxo Complex
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https://figshare.com/articles/dataset/Structural_Characterization_and_Oxidation_Reactivity_of_a_Nickel_II_Acylperoxo_Complex/2421463
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资源简介：
The
nickel(II)–acylperoxo complex [Ni(TpCF3Me)(κ2-mCPBA)] (1CF3Me) [TpCF3Me = hydrotris(3-trifluoromethyl-5-methylpyrazolyl)borate, mCPBA = m-chloroperbenzoate] was isolated
and fully characterized. The electrophilic oxygenation ability of 1CF3Me toward sulfides
and olefins was confirmed. The Michaelis–Menten-type behavior
of thioanisole oxygenation indicates the existence of a pre-equilibrium
of substrate association in the reaction. In addition, 1CF3Me retains H-atom abstraction ability for
hydrocarbons with activated methylene C–H bonds (e.g., fluorene).
The oxidations of styrenes and these readily oxidizable hydrocarbons
follow second-order kinetics, first-order each with respect to 1CF3Me and substrate. The lack of clear
acceleration in the decay of 1CF3Me in the presence of substrates with high C–H
bond dissociation energies (e.g., cyclohexane) suggests that another
reaction pathway contributes through the O–O-cleaved intermediate.
创建时间：
2016-02-19
