Pincer‐Supported Perfluororhodacyclopentanes: High Nucleophilicity of the M−C F Bond
Perfluororhodacyclopentane supported by PBP pincer ligand PBP‐Rh III (CF 2 ) 4 ( 2 ) was prepared from PBP‐Rh I ‐PPh 3 ( 1 ) and tetrafluoroethylene (TFE). By scXRD analysis, it was revealed that the Rh−C F bond trans to the boryl ligand was largely elongated compared to the one in the apical positi...
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| Veröffentlicht in: | Angewandte Chemie International Edition 2022-09, Vol.61 (37) |
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| creator | Hayashi, Shinya Murayama, Toshiki Kusumoto, Shuhei Nozaki, Kyoko |
| description | Perfluororhodacyclopentane supported by PBP pincer ligand PBP‐Rh
III
(CF
2
)
4
(
2
) was prepared from PBP‐Rh
I
‐PPh
3
(
1
) and tetrafluoroethylene (TFE). By scXRD analysis, it was revealed that the Rh−C
F
bond trans to the boryl ligand was largely elongated compared to the one in the apical position. Although M−C
F
bonds of perfluorometallacyclopentanes are known to be very stable,
2
shows high reactivity toward hydrogenolysis, iodinolysis and protonolysis, thanks to the strong trans‐effect of the highly σ‐donating boryl ligand. Analogous PCP pincer complex PCP−Rh
III
(CF
2
)
4
(
4
) showed slower reaction rate both in oxidative cyclization with TFE and hydrogenolysis of Rh−C
F
bond. Catalytic production of 1,1,2,2,3,3,4,4‐octafluorobutane from two TFE and hydrogen in one pot was achieved via repetitive oxidative cyclization of TFE and Rh followed by the hydrogenolysis of Rh−C
F
bonds. This report demonstrates the possible application of PBP‐pincer skeleton to the preparation of fluorinated compounds from TFE. |
| doi_str_mv | 10.1002/anie.202207760 |
| format | Article |
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III
(CF
2
)
4
(
2
) was prepared from PBP‐Rh
I
‐PPh
3
(
1
) and tetrafluoroethylene (TFE). By scXRD analysis, it was revealed that the Rh−C
F
bond trans to the boryl ligand was largely elongated compared to the one in the apical position. Although M−C
F
bonds of perfluorometallacyclopentanes are known to be very stable,
2
shows high reactivity toward hydrogenolysis, iodinolysis and protonolysis, thanks to the strong trans‐effect of the highly σ‐donating boryl ligand. Analogous PCP pincer complex PCP−Rh
III
(CF
2
)
4
(
4
) showed slower reaction rate both in oxidative cyclization with TFE and hydrogenolysis of Rh−C
F
bond. Catalytic production of 1,1,2,2,3,3,4,4‐octafluorobutane from two TFE and hydrogen in one pot was achieved via repetitive oxidative cyclization of TFE and Rh followed by the hydrogenolysis of Rh−C
F
bonds. This report demonstrates the possible application of PBP‐pincer skeleton to the preparation of fluorinated compounds from TFE.</description><identifier>ISSN: 1433-7851</identifier><identifier>EISSN: 1521-3773</identifier><identifier>DOI: 10.1002/anie.202207760</identifier><language>eng</language><ispartof>Angewandte Chemie International Edition, 2022-09, Vol.61 (37)</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c169t-865ff60aadc870593c01d69d64436ebb4eb3537681c869bc8488e16b92d5b7e33</citedby><cites>FETCH-LOGICAL-c169t-865ff60aadc870593c01d69d64436ebb4eb3537681c869bc8488e16b92d5b7e33</cites><orcidid>0000-0002-0364-0471 ; 0000-0002-4743-4784 ; 0000-0002-0321-5299</orcidid></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>Hayashi, Shinya</creatorcontrib><creatorcontrib>Murayama, Toshiki</creatorcontrib><creatorcontrib>Kusumoto, Shuhei</creatorcontrib><creatorcontrib>Nozaki, Kyoko</creatorcontrib><title>Pincer‐Supported Perfluororhodacyclopentanes: High Nucleophilicity of the M−C F Bond</title><title>Angewandte Chemie International Edition</title><description>Perfluororhodacyclopentane supported by PBP pincer ligand PBP‐Rh
III
(CF
2
)
4
(
2
) was prepared from PBP‐Rh
I
‐PPh
3
(
1
) and tetrafluoroethylene (TFE). By scXRD analysis, it was revealed that the Rh−C
F
bond trans to the boryl ligand was largely elongated compared to the one in the apical position. Although M−C
F
bonds of perfluorometallacyclopentanes are known to be very stable,
2
shows high reactivity toward hydrogenolysis, iodinolysis and protonolysis, thanks to the strong trans‐effect of the highly σ‐donating boryl ligand. Analogous PCP pincer complex PCP−Rh
III
(CF
2
)
4
(
4
) showed slower reaction rate both in oxidative cyclization with TFE and hydrogenolysis of Rh−C
F
bond. Catalytic production of 1,1,2,2,3,3,4,4‐octafluorobutane from two TFE and hydrogen in one pot was achieved via repetitive oxidative cyclization of TFE and Rh followed by the hydrogenolysis of Rh−C
F
bonds. This report demonstrates the possible application of PBP‐pincer skeleton to the preparation of fluorinated compounds from TFE.</description><issn>1433-7851</issn><issn>1521-3773</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2022</creationdate><recordtype>article</recordtype><recordid>eNo90L1OwzAcBHALgUQprMx-gQQ7jj_CBhFtkQpUAiS2yLH_IUYhjpxkyMbIiHjEPgmtQEx3w-mGH0LnlMSUkORCtw7ihCQJkVKQAzSjPKERk5Id7nrKWCQVp8fopO_fdnuliJihl41rDYTtx9fj2HU-DGDxBkLVjD74UHurzWQa30E76Bb6S7xyrzW-H00Dvqtd44wbJuwrPNSA77af3zle4Gvf2lN0VOmmh7O_nKPnxc1TvorWD8vb_GodGSqyIVKCV5UgWlujJOEZM4RakVmRpkxAWaZQMs6kUNQokZVGpUoBFWWWWF5KYGyO4t9fE3zfB6iKLrh3HaaCkmLvUuxdin8X9gMxAVkE</recordid><startdate>20220912</startdate><enddate>20220912</enddate><creator>Hayashi, Shinya</creator><creator>Murayama, Toshiki</creator><creator>Kusumoto, Shuhei</creator><creator>Nozaki, Kyoko</creator><scope>AAYXX</scope><scope>CITATION</scope><orcidid>https://orcid.org/0000-0002-0364-0471</orcidid><orcidid>https://orcid.org/0000-0002-4743-4784</orcidid><orcidid>https://orcid.org/0000-0002-0321-5299</orcidid></search><sort><creationdate>20220912</creationdate><title>Pincer‐Supported Perfluororhodacyclopentanes: High Nucleophilicity of the M−C F Bond</title><author>Hayashi, Shinya ; Murayama, Toshiki ; Kusumoto, Shuhei ; Nozaki, Kyoko</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c169t-865ff60aadc870593c01d69d64436ebb4eb3537681c869bc8488e16b92d5b7e33</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2022</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Hayashi, Shinya</creatorcontrib><creatorcontrib>Murayama, Toshiki</creatorcontrib><creatorcontrib>Kusumoto, Shuhei</creatorcontrib><creatorcontrib>Nozaki, Kyoko</creatorcontrib><collection>CrossRef</collection><jtitle>Angewandte Chemie International Edition</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Hayashi, Shinya</au><au>Murayama, Toshiki</au><au>Kusumoto, Shuhei</au><au>Nozaki, Kyoko</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Pincer‐Supported Perfluororhodacyclopentanes: High Nucleophilicity of the M−C F Bond</atitle><jtitle>Angewandte Chemie International Edition</jtitle><date>2022-09-12</date><risdate>2022</risdate><volume>61</volume><issue>37</issue><issn>1433-7851</issn><eissn>1521-3773</eissn><abstract>Perfluororhodacyclopentane supported by PBP pincer ligand PBP‐Rh
III
(CF
2
)
4
(
2
) was prepared from PBP‐Rh
I
‐PPh
3
(
1
) and tetrafluoroethylene (TFE). By scXRD analysis, it was revealed that the Rh−C
F
bond trans to the boryl ligand was largely elongated compared to the one in the apical position. Although M−C
F
bonds of perfluorometallacyclopentanes are known to be very stable,
2
shows high reactivity toward hydrogenolysis, iodinolysis and protonolysis, thanks to the strong trans‐effect of the highly σ‐donating boryl ligand. Analogous PCP pincer complex PCP−Rh
III
(CF
2
)
4
(
4
) showed slower reaction rate both in oxidative cyclization with TFE and hydrogenolysis of Rh−C
F
bond. Catalytic production of 1,1,2,2,3,3,4,4‐octafluorobutane from two TFE and hydrogen in one pot was achieved via repetitive oxidative cyclization of TFE and Rh followed by the hydrogenolysis of Rh−C
F
bonds. This report demonstrates the possible application of PBP‐pincer skeleton to the preparation of fluorinated compounds from TFE.</abstract><doi>10.1002/anie.202207760</doi><orcidid>https://orcid.org/0000-0002-0364-0471</orcidid><orcidid>https://orcid.org/0000-0002-4743-4784</orcidid><orcidid>https://orcid.org/0000-0002-0321-5299</orcidid></addata></record> |
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| language | eng |
| recordid | cdi_crossref_primary_10_1002_anie_202207760 |
| source | Wiley Online Library All Journals |
| title | Pincer‐Supported Perfluororhodacyclopentanes: High Nucleophilicity of the M−C F Bond |
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