Structure and Unprecedented Reactivity of a Mononuclear Nonheme Cobalt(III) Iodosylbenzene Complex

Jindou Yang, Mi Sook Seo, Kyung Ha Kim, Yong Min Lee, Shunichi Fukuzumi, Jason Shearer, Wonwoo Nam

Research output: Contribution to journalArticlepeer-review

18 Scopus citations

Abstract

A mononuclear nonheme cobalt(III) iodosylbenzene complex, [CoIII(TQA)(OIPh)(OH)]2+ (1), is synthesized and characterized structurally and spectroscopically. While 1 is a sluggish oxidant in oxidation reactions, it becomes a competent oxidant in oxygen atom transfer reactions, such as olefin epoxidation, in the presence of a small amount of proton. More interestingly, 1 shows a nucleophilic reactivity in aldehyde deformylation reaction, demonstrating that 1 has an amphoteric reactivity. Another interesting observation is that 1 can be used as an oxygen atom donor in the generation of high-valent metal-oxo complexes. To our knowledge, we present the first crystal structure of a CoIII iodosylbenzene complex and the unprecedented reactivity of metal-iodosylarene adduct.

Original languageEnglish
Pages (from-to)13581-13585
Number of pages5
JournalAngewandte Chemie - International Edition
Volume59
Issue number32
DOIs
StatePublished - 3 Aug 2020

Bibliographical note

Funding Information:
This work was supported by the NRF of Korea through CRI (NRF‐2012R1A3A2048842 to W.N.), Basic Science Research Program (2017R1D1A1B03029982 to Y.‐M.L., 2017R1D1A1B03032615 to S.F., and 2019R1I1A1A01055822 to M.S.S.) and the NSF of USA (CHE‐1900380 and CHE‐1854854 to J.S.). X‐ray absorption data were collected on beamline 07ID‐2 at the Canadian Light Source, which is supported by the CFI, NSERC, NRC, CIHR, the Government of Saskatchewan, and the University of Saskatchewan.

Funding Information:
This work was supported by the NRF of Korea through CRI (NRF-2012R1A3A2048842 to W.N.), Basic Science Research Program (2017R1D1A1B03029982 to Y.-M.L., 2017R1D1A1B03032615 to S.F., and 2019R1I1A1A01055822 to M.S.S.) and the NSF of USA (CHE-1900380 and CHE-1854854 to J.S.). X-ray absorption data were collected on beamline 07ID-2 at the Canadian Light Source, which is supported by the CFI, NSERC, NRC, CIHR, the Government of Saskatchewan, and the University of Saskatchewan.

Publisher Copyright:
© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Keywords

  • aldehyde deformylation reaction
  • amphoteric reactivity
  • cobalt(III) complexes
  • iodosylbenzene adducts
  • nonheme complexes

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