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

Hao Ching Chang, Sheng Hsiang Lin, Yu Chen Hsu, Shao Wei Jen, Way-Zen Lee

Research output: Contribution to journalArticle

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.

Original languageEnglish
Pages (from-to)3796-3802
Number of pages7
JournalDalton Transactions
Volume47
Issue number11
DOIs
Publication statusPublished - 2018 Jan 1

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Bearings (structural)
Nickel
Sulfhydryl Compounds
Deprotonation
Discrete Fourier transforms
Amines
Paramagnetic resonance
Protons
Absorption spectra
Electrons
Oxidation
Temperature

ASJC Scopus subject areas

  • Inorganic Chemistry

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Nickel(III)-mediated oxidatIVe cascades from a thiol-bearing nickel(II) precursor to the nickel(IV) product. / Chang, Hao Ching; Lin, Sheng Hsiang; Hsu, Yu Chen; Jen, Shao Wei; Lee, Way-Zen.

In: Dalton Transactions, Vol. 47, No. 11, 01.01.2018, p. 3796-3802.

Research output: Contribution to journalArticle

Chang, Hao Ching ; Lin, Sheng Hsiang ; Hsu, Yu Chen ; Jen, Shao Wei ; Lee, Way-Zen. / Nickel(III)-mediated oxidatIVe cascades from a thiol-bearing nickel(II) precursor to the nickel(IV) product. In: Dalton Transactions. 2018 ; Vol. 47, No. 11. pp. 3796-3802.
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