Synthesis and Reactivity of the Fluoro Complex trans-[Pd(F)(4-C5NF4)( i Pr2PCH2CH2OCH3)2]: C–F Bond Formation and Catalytic C–F Bond Activation Reactions
The reaction of [Pd(Me)2(tmeda)] (tmeda = N,N,N′,N′-tetramethylethylendiamine) with the phosphine i Pr2PCH2CH2OCH3 resulted in the formation of the palladium(0) complex [Pd( i Pr2PCH2CH2OCH3)2] (1). Treatment of 1 with pentafluoropyridine at room temperature yielded the C–F activation product trans-...
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| Veröffentlicht in: | Organometallics 2012-02, Vol.31 (4), p.1417-1424 |
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| creator | Breyer, David Braun, Thomas Kläring, Paul |
| description | The reaction of [Pd(Me)2(tmeda)] (tmeda = N,N,N′,N′-tetramethylethylendiamine) with the phosphine i Pr2PCH2CH2OCH3 resulted in the formation of the palladium(0) complex [Pd( i Pr2PCH2CH2OCH3)2] (1). Treatment of 1 with pentafluoropyridine at room temperature yielded the C–F activation product trans-[Pd(F)(4-C5NF4)( i Pr2PCH2CH2OCH3)2] (2). The triflato and bromo complexes trans-[Pd(OTf)(4-C5NF4)( i Pr2PCH2CH2OCH3)2] (4) and trans-[Pd(Br)(4-C5NF4)( i Pr2PCH2CH2OCH3)2] (5) could be prepared on reaction of complex 2 with EtOTf or 3-bromopropene, respectively. Treatment of 2 with Me3SiCl or HBpin (HBpin = 4,4,5,5-tetramethyl-1,3,2-dioxaborolane, pinacolborane) effects the formation of trans-[Pd(Cl)(4-C5NF4)( i Pr2PCH2CH2OCH3)2] (6) and trans-[Pd(H)(4-C5NF4)( i Pr2PCH2CH2OCH3)2] (7). In catalytic experiments pentafluoropyridine could be converted into the 4-aryl-tetrafluoropyridines (8, aryl = Ph; 9, aryl = Tol) and into 2,3,5,6-tetrafluoropyridine in the presence of the boronic acids PhB(OH)2, TolB(OH)2, or HBpin when 5 mol % of 2 is employed as catalyst. |
| doi_str_mv | 10.1021/om200998d |
| format | Article |
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Treatment of 1 with pentafluoropyridine at room temperature yielded the C–F activation product trans-[Pd(F)(4-C5NF4)( i Pr2PCH2CH2OCH3)2] (2). The triflato and bromo complexes trans-[Pd(OTf)(4-C5NF4)( i Pr2PCH2CH2OCH3)2] (4) and trans-[Pd(Br)(4-C5NF4)( i Pr2PCH2CH2OCH3)2] (5) could be prepared on reaction of complex 2 with EtOTf or 3-bromopropene, respectively. Treatment of 2 with Me3SiCl or HBpin (HBpin = 4,4,5,5-tetramethyl-1,3,2-dioxaborolane, pinacolborane) effects the formation of trans-[Pd(Cl)(4-C5NF4)( i Pr2PCH2CH2OCH3)2] (6) and trans-[Pd(H)(4-C5NF4)( i Pr2PCH2CH2OCH3)2] (7). In catalytic experiments pentafluoropyridine could be converted into the 4-aryl-tetrafluoropyridines (8, aryl = Ph; 9, aryl = Tol) and into 2,3,5,6-tetrafluoropyridine in the presence of the boronic acids PhB(OH)2, TolB(OH)2, or HBpin when 5 mol % of 2 is employed as catalyst.</description><identifier>ISSN: 0276-7333</identifier><identifier>EISSN: 1520-6041</identifier><identifier>DOI: 10.1021/om200998d</identifier><language>eng</language><publisher>American Chemical Society</publisher><ispartof>Organometallics, 2012-02, Vol.31 (4), p.1417-1424</ispartof><rights>Copyright © 2012 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a325t-cdc49e084e37922c2a69ed1eead6d24f48a110f10c0e4285b799320bd00ca0d73</citedby><cites>FETCH-LOGICAL-a325t-cdc49e084e37922c2a69ed1eead6d24f48a110f10c0e4285b799320bd00ca0d73</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/om200998d$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/om200998d$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,776,780,2751,27055,27903,27904,56716,56766</link.rule.ids></links><search><creatorcontrib>Breyer, David</creatorcontrib><creatorcontrib>Braun, Thomas</creatorcontrib><creatorcontrib>Kläring, Paul</creatorcontrib><title>Synthesis and Reactivity of the Fluoro Complex trans-[Pd(F)(4-C5NF4)( i Pr2PCH2CH2OCH3)2]: C–F Bond Formation and Catalytic C–F Bond Activation Reactions</title><title>Organometallics</title><addtitle>Organometallics</addtitle><description>The reaction of [Pd(Me)2(tmeda)] (tmeda = N,N,N′,N′-tetramethylethylendiamine) with the phosphine i Pr2PCH2CH2OCH3 resulted in the formation of the palladium(0) complex [Pd( i Pr2PCH2CH2OCH3)2] (1). Treatment of 1 with pentafluoropyridine at room temperature yielded the C–F activation product trans-[Pd(F)(4-C5NF4)( i Pr2PCH2CH2OCH3)2] (2). The triflato and bromo complexes trans-[Pd(OTf)(4-C5NF4)( i Pr2PCH2CH2OCH3)2] (4) and trans-[Pd(Br)(4-C5NF4)( i Pr2PCH2CH2OCH3)2] (5) could be prepared on reaction of complex 2 with EtOTf or 3-bromopropene, respectively. Treatment of 2 with Me3SiCl or HBpin (HBpin = 4,4,5,5-tetramethyl-1,3,2-dioxaborolane, pinacolborane) effects the formation of trans-[Pd(Cl)(4-C5NF4)( i Pr2PCH2CH2OCH3)2] (6) and trans-[Pd(H)(4-C5NF4)( i Pr2PCH2CH2OCH3)2] (7). In catalytic experiments pentafluoropyridine could be converted into the 4-aryl-tetrafluoropyridines (8, aryl = Ph; 9, aryl = Tol) and into 2,3,5,6-tetrafluoropyridine in the presence of the boronic acids PhB(OH)2, TolB(OH)2, or HBpin when 5 mol % of 2 is employed as catalyst.</description><issn>0276-7333</issn><issn>1520-6041</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2012</creationdate><recordtype>article</recordtype><recordid>eNptkE9Kw0AYxQdRsFYX3mA2QrOIfjOTv-5qMFYotvhnJRKmMxNMSTJlJhWz8w4ewBN4CY_iSUyNiAvhg7f4frz3eAgdEjgmQMmJrihAHEdyCw2IT8ENwCPbaAA0DNyQMbaL9qxdAkAQMjpAbzdt3TwqW1jMa4mvFRdN8VQ0LdY57h44LdfaaJzoalWqZ9wYXlv3fi5HqTPy3MS_Sj3n432ECzw3dJ5MaHezZMIc-nCKk8-X1xSf6c451abiTaHr75yEN7xsm0L8Rcab6J7pe-ja7qOdnJdWHfzoEN2l57fJxJ3OLi6T8dTljPqNK6TwYgWRp1gYUyooD2IliVJcBpJ6uRdxQiAnIEB5NPIXYRwzCgsJIDjIkA2R0_sKo601Ks9Wpqi4aTMC2WbZ7HfZjj3qWS5sttRrU3fN_uG-AHHod9M</recordid><startdate>20120227</startdate><enddate>20120227</enddate><creator>Breyer, David</creator><creator>Braun, Thomas</creator><creator>Kläring, Paul</creator><general>American Chemical Society</general><scope>AAYXX</scope><scope>CITATION</scope></search><sort><creationdate>20120227</creationdate><title>Synthesis and Reactivity of the Fluoro Complex trans-[Pd(F)(4-C5NF4)( i Pr2PCH2CH2OCH3)2]: C–F Bond Formation and Catalytic C–F Bond Activation Reactions</title><author>Breyer, David ; Braun, Thomas ; Kläring, Paul</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a325t-cdc49e084e37922c2a69ed1eead6d24f48a110f10c0e4285b799320bd00ca0d73</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2012</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Breyer, David</creatorcontrib><creatorcontrib>Braun, Thomas</creatorcontrib><creatorcontrib>Kläring, Paul</creatorcontrib><collection>CrossRef</collection><jtitle>Organometallics</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Breyer, David</au><au>Braun, Thomas</au><au>Kläring, Paul</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Synthesis and Reactivity of the Fluoro Complex trans-[Pd(F)(4-C5NF4)( i Pr2PCH2CH2OCH3)2]: C–F Bond Formation and Catalytic C–F Bond Activation Reactions</atitle><jtitle>Organometallics</jtitle><addtitle>Organometallics</addtitle><date>2012-02-27</date><risdate>2012</risdate><volume>31</volume><issue>4</issue><spage>1417</spage><epage>1424</epage><pages>1417-1424</pages><issn>0276-7333</issn><eissn>1520-6041</eissn><abstract>The reaction of [Pd(Me)2(tmeda)] (tmeda = N,N,N′,N′-tetramethylethylendiamine) with the phosphine i Pr2PCH2CH2OCH3 resulted in the formation of the palladium(0) complex [Pd( i Pr2PCH2CH2OCH3)2] (1). Treatment of 1 with pentafluoropyridine at room temperature yielded the C–F activation product trans-[Pd(F)(4-C5NF4)( i Pr2PCH2CH2OCH3)2] (2). The triflato and bromo complexes trans-[Pd(OTf)(4-C5NF4)( i Pr2PCH2CH2OCH3)2] (4) and trans-[Pd(Br)(4-C5NF4)( i Pr2PCH2CH2OCH3)2] (5) could be prepared on reaction of complex 2 with EtOTf or 3-bromopropene, respectively. Treatment of 2 with Me3SiCl or HBpin (HBpin = 4,4,5,5-tetramethyl-1,3,2-dioxaborolane, pinacolborane) effects the formation of trans-[Pd(Cl)(4-C5NF4)( i Pr2PCH2CH2OCH3)2] (6) and trans-[Pd(H)(4-C5NF4)( i Pr2PCH2CH2OCH3)2] (7). In catalytic experiments pentafluoropyridine could be converted into the 4-aryl-tetrafluoropyridines (8, aryl = Ph; 9, aryl = Tol) and into 2,3,5,6-tetrafluoropyridine in the presence of the boronic acids PhB(OH)2, TolB(OH)2, or HBpin when 5 mol % of 2 is employed as catalyst.</abstract><pub>American Chemical Society</pub><doi>10.1021/om200998d</doi><tpages>8</tpages></addata></record> |
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| source | ACS Publications |
| title | Synthesis and Reactivity of the Fluoro Complex trans-[Pd(F)(4-C5NF4)( i Pr2PCH2CH2OCH3)2]: C–F Bond Formation and Catalytic C–F Bond Activation Reactions |
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