A discrete {Co4(μ3-OH)4}4+ cluster with an oxygen-rich coordination environment as a catalyst for the epoxidation of various olefinsElectronic supplementary information (ESI) available. CCDC 1408240. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5dt03422a
Using the sterically hindered terphenyl-based carboxylate, the tetrameric Co( ii ) complex [Co 4 (μ 3 -OH) 4 (μ-O 2 CAr 4F-Ph ) 2 (μ-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 paramagn...
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creator | Lee, Sun Young Kim, Namseok Lee, Myoung Mi Jo, Young Dan Bae, Jeong Mi Hyun, Min Young Yoon, Sungho Kim, Cheal |
description | Using the sterically hindered terphenyl-based carboxylate, the tetrameric Co(
ii
) complex [Co
4
(μ
3
-OH)
4
(μ-O
2
CAr
4F-Ph
)
2
(μ-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, H
2
18
O-exchange experiments, and EPR studies, it has been proposed that multiple reactive cobalt-oxo species Co
V
&z.dbd;O and Co
IV
&z.dbd;O were involved in the olefin epoxidation.
A tetranuclear Co(
ii
) complex was active for epoxidation reactions of various olefins, and Co
V
&z.dbd;O and Co
IV
&z.dbd;O species were proposed to be the possible reactive intermediates. |
doi_str_mv | 10.1039/c5dt03422a |
format | Article |
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ii
) complex [Co
4
(μ
3
-OH)
4
(μ-O
2
CAr
4F-Ph
)
2
(μ-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, H
2
18
O-exchange experiments, and EPR studies, it has been proposed that multiple reactive cobalt-oxo species Co
V
&z.dbd;O and Co
IV
&z.dbd;O were involved in the olefin epoxidation.
A tetranuclear Co(
ii
) complex was active for epoxidation reactions of various olefins, and Co
V
&z.dbd;O and Co
IV
&z.dbd;O species were proposed to be the possible reactive intermediates.</description><identifier>ISSN: 1477-9226</identifier><identifier>EISSN: 1477-9234</identifier><identifier>DOI: 10.1039/c5dt03422a</identifier><creationdate>2016-01</creationdate><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>315,781,785,27929,27930</link.rule.ids></links><search><creatorcontrib>Lee, Sun Young</creatorcontrib><creatorcontrib>Kim, Namseok</creatorcontrib><creatorcontrib>Lee, Myoung Mi</creatorcontrib><creatorcontrib>Jo, Young Dan</creatorcontrib><creatorcontrib>Bae, Jeong Mi</creatorcontrib><creatorcontrib>Hyun, Min Young</creatorcontrib><creatorcontrib>Yoon, Sungho</creatorcontrib><creatorcontrib>Kim, Cheal</creatorcontrib><title>A discrete {Co4(μ3-OH)4}4+ cluster with an oxygen-rich coordination environment as a catalyst for the epoxidation of various olefinsElectronic supplementary information (ESI) available. CCDC 1408240. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5dt03422a</title><description>Using the sterically hindered terphenyl-based carboxylate, the tetrameric Co(
ii
) complex [Co
4
(μ
3
-OH)
4
(μ-O
2
CAr
4F-Ph
)
2
(μ-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, H
2
18
O-exchange experiments, and EPR studies, it has been proposed that multiple reactive cobalt-oxo species Co
V
&z.dbd;O and Co
IV
&z.dbd;O were involved in the olefin epoxidation.
A tetranuclear Co(
ii
) complex was active for epoxidation reactions of various olefins, and Co
V
&z.dbd;O and Co
IV
&z.dbd;O species were proposed to be the possible reactive intermediates.</description><issn>1477-9226</issn><issn>1477-9234</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2016</creationdate><recordtype>article</recordtype><sourceid/><recordid>eNqFkE1PAjEQhlejifhx8W4yR4hZ7HaLiDezQODEQe9k7M6yNaXdtAUhxn_mb_A3WYORgwdP02TePs-bSZLLjHUzlg9uZK8MLBec42HSykS_nw54Lo5-3_z2JDn1_oUxzlmPtw7aD1AqLx0FgrfCivbnR57OJh3xLq5B6pUP5OBVhRrQgN1sF2RSp2QN0lpXKoNBWQNk1spZsyQTAD0gSAyotz5AZR2EmoAau1HlLm0rWKNTduXBaqqU8SNNMkSAkuBXTaPpm4RuC8pEwHL3rT16nHYA16g0PmvqQlEMC8gEu-OCdWEcTTERe5YgXXSj1nbhsKkjNZoxwqCYjiHmbKzkgPbWnQU8EQxn03v4e8_z5LhC7eniZ54lV-PRUzFJnZfzxqllrDvfx_P_9l-Scoof</recordid><startdate>20160119</startdate><enddate>20160119</enddate><creator>Lee, Sun Young</creator><creator>Kim, Namseok</creator><creator>Lee, Myoung Mi</creator><creator>Jo, Young Dan</creator><creator>Bae, Jeong Mi</creator><creator>Hyun, Min Young</creator><creator>Yoon, Sungho</creator><creator>Kim, Cheal</creator><scope/></search><sort><creationdate>20160119</creationdate><title>A discrete {Co4(μ3-OH)4}4+ cluster with an oxygen-rich coordination environment as a catalyst for the epoxidation of various olefinsElectronic supplementary information (ESI) available. CCDC 1408240. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5dt03422a</title><author>Lee, Sun Young ; Kim, Namseok ; Lee, Myoung Mi ; Jo, Young Dan ; Bae, Jeong Mi ; Hyun, Min Young ; Yoon, Sungho ; Kim, Cheal</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-rsc_primary_c5dt03422a3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><creationdate>2016</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Lee, Sun Young</creatorcontrib><creatorcontrib>Kim, Namseok</creatorcontrib><creatorcontrib>Lee, Myoung Mi</creatorcontrib><creatorcontrib>Jo, Young Dan</creatorcontrib><creatorcontrib>Bae, Jeong Mi</creatorcontrib><creatorcontrib>Hyun, Min Young</creatorcontrib><creatorcontrib>Yoon, Sungho</creatorcontrib><creatorcontrib>Kim, Cheal</creatorcontrib></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Lee, Sun Young</au><au>Kim, Namseok</au><au>Lee, Myoung Mi</au><au>Jo, Young Dan</au><au>Bae, Jeong Mi</au><au>Hyun, Min Young</au><au>Yoon, Sungho</au><au>Kim, Cheal</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>A discrete {Co4(μ3-OH)4}4+ cluster with an oxygen-rich coordination environment as a catalyst for the epoxidation of various olefinsElectronic supplementary information (ESI) available. CCDC 1408240. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5dt03422a</atitle><date>2016-01-19</date><risdate>2016</risdate><volume>45</volume><issue>4</issue><spage>1727</spage><epage>1736</epage><pages>1727-1736</pages><issn>1477-9226</issn><eissn>1477-9234</eissn><abstract>Using the sterically hindered terphenyl-based carboxylate, the tetrameric Co(
ii
) complex [Co
4
(μ
3
-OH)
4
(μ-O
2
CAr
4F-Ph
)
2
(μ-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, H
2
18
O-exchange experiments, and EPR studies, it has been proposed that multiple reactive cobalt-oxo species Co
V
&z.dbd;O and Co
IV
&z.dbd;O were involved in the olefin epoxidation.
A tetranuclear Co(
ii
) complex was active for epoxidation reactions of various olefins, and Co
V
&z.dbd;O and Co
IV
&z.dbd;O species were proposed to be the possible reactive intermediates.</abstract><doi>10.1039/c5dt03422a</doi><tpages>1</tpages></addata></record> |
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source | Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
title | A discrete {Co4(μ3-OH)4}4+ cluster with an oxygen-rich coordination environment as a catalyst for the epoxidation of various olefinsElectronic supplementary information (ESI) available. CCDC 1408240. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5dt03422a |
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