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

研究成果: 雜誌貢獻期刊論文同行評審

3 引文 斯高帕斯(Scopus)

摘要

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.

原文英語
頁(從 - 到)3796-3802
頁數7
期刊Dalton Transactions
47
發行號11
DOIs
出版狀態已發佈 - 2018

ASJC Scopus subject areas

  • 無機化學

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