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Nickel(III)-mediated oxidatIVe cascades from a thiol-bearing nickel(II) precursor to the nickel(IV) product

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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.

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Chang, H. C., Lin, S. H., Hsu, Y. C., Jen, S. W., & Lee, W. Z. (2018). Nickel(III)-mediated oxidatIVe cascades from a thiol-bearing nickel(II) precursor to the nickel(IV) product. Dalton Transactions, 47(11), 3796–3802. https://doi.org/10.1039/c7dt04137c

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