A discrete {Co4(μ(3)-OH)(4)}(4+) cluster with an oxygen-rich coordination environment as a catalyst for the epoxidation of various olefins
- Authors
- Lee, Sun Young; Kim, Namseok; Lee, Myoung Mi; Jo, Young Dan; Bae, Jeong Mi; Hyun, Min Young; Yoon, Sungho; Kim, Cheal
- Issue Date
- Jan-2016
- Publisher
- ROYAL SOC CHEMISTRY
- Citation
- DALTON TRANSACTIONS, v.45, no.4, pp 1727 - 1736
- Pages
- 10
- Journal Title
- DALTON TRANSACTIONS
- Volume
- 45
- Number
- 4
- Start Page
- 1727
- End Page
- 1736
- URI
- https://scholarworks.bwise.kr/cau/handle/2019.sw.cau/45702
- DOI
- 10.1039/c5dt03422a
- ISSN
- 1477-9226
1477-9234
- Abstract
- Using the sterically hindered terphenyl-based carboxylate, the tetrameric Co(II) complex [Co-4(mu(3)-OH)(4)(mu-O2CAr4F-Ph)(2)(mu-OTf)(2)(Py)(4)] (1) with an asymmetric cubane-type core has been synthesized and fully characterized by X-ray diffraction, UV-vis spectroscopy, and electron paramagnetic resonance spectroscopy. Interestingly, the cubane-type cobalt cluster 1 with 3-chloroperoxybenzoic acid as the oxidant was found to be very effective in the epoxidation of a variety of olefins, including terminal olefins which are more challenging targeting substrates. Moreover, this catalytic system showed a fast reaction rate and high epoxide yields under mild conditions. Based on product analysis and Hammett studies, the use of peroxyphenylacetic acid as a mechanistic probe, (H2O)-O-18-exchange experiments, and EPR studies, it has been proposed that multiple reactive cobalt-oxo species Co-V=O and Co-IV=O were involved in the olefin epoxidation.
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