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- W2787249350 abstract "A nickel(ii) complex, Ni(HPS2)2 (1) that contains two pendant thiols, is rapidly aerobically oxidized in the presence of an amine to produce a diamagnetic nickel(iv) complex, Ni(PS2)2 (2). This process was investigated spectroscopically at a temperature of -80 °C. Absorption spectra revealed that the deprotonation of one pendant thiol of 1 triggers an oxidative cascade; EPR findings indicate that single-spin species comprised of nickel(iii) intermediates are produced in the reaction solution. Possible reaction routes were examined by DFT calculations, in which an energy profile indicates that (i) a self-driven formation of 2 favors a sequential proton/electron transfer pathway; (ii) kinetically trapped nickel(iii) intermediates may respond to the specificity of the coordination of 2 in a cis-form. The overall findings help one to rationalize how a nickel(ii) precursor can be oxidized by O2 to a higher oxidation state." @default.
- W2787249350 created "2018-02-23" @default.
- W2787249350 creator A5049062759 @default.
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- W2787249350 creator A5079510617 @default.
- W2787249350 creator A5081089331 @default.
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- W2787249350 date "2018-01-01" @default.
- W2787249350 modified "2023-10-13" @default.
- W2787249350 title "Nickel(<scp>iii</scp>)-mediated oxidative cascades from a thiol-bearing nickel(<scp>ii</scp>) precursor to the nickel(<scp>iv</scp>) product" @default.
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- W2787249350 doi "https://doi.org/10.1039/c7dt04137c" @default.
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