The electron-poor phosphines P{C6H3(CF3)2-3,5}3 and P(C6F5)3 do not mimic phosphites as ligands for hydroformylation. A comparison of the coordination chemistry of P{C6H3(CF3)2-3,5}3 and P(C6F5)3 and the unexpectedly low hydroformylation activity of their rhodium complexes

The electron-poor phosphines P{C6H3(CF3)2-3,5}3 and P(C6F5)3 do not mimic phosphites as ligands for hydroformylation. A comparison of the coordination chemistry of P{C6H3(CF3)2-3,5}3 and P(C6F5)3 and the unexpectedly low hydroformylation activity of their rhodium complexes

The fluoroaryl phosphines P{C6H3(CF3)2-3,5}3 (La) and P(C6F5)3 (Lb) form the complexes trans-[MCl2(La)2] and trans-[MCl2(Lb)2](M = Pd or Pt) which have been isolated and fully characterised. 31P NMR studies of competition experiments show that the stability of trans-[PdCl2L2] is in the order L = Lb&...

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Veröffentlicht in:Dalton transactions : an international journal of inorganic chemistry 2005-04 (7), p.1294-1300
Hauptverfasser: Clarke, Matthew L, Ellis, Dianne, Mason, Kate L, Orpen, A Guy, Pringle, Paul G, Wingad, Richard L, Zaher, Damien A, Baker, R Tom
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container_title Dalton transactions : an international journal of inorganic chemistry
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creator Clarke, Matthew L
Ellis, Dianne
Mason, Kate L
Orpen, A Guy
Pringle, Paul G
Wingad, Richard L
Zaher, Damien A
Baker, R Tom
description The fluoroaryl phosphines P{C6H3(CF3)2-3,5}3 (La) and P(C6F5)3 (Lb) form the complexes trans-[MCl2(La)2] and trans-[MCl2(Lb)2](M = Pd or Pt) which have been isolated and fully characterised. 31P NMR studies of competition experiments show that the stability of trans-[PdCl2L2] is in the order L = Lb< La
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A comparison of the coordination chemistry of P{C6H3(CF3)2-3,5}3 and P(C6F5)3 and the unexpectedly low hydroformylation activity of their rhodium complexes</title><source>Royal Society Of Chemistry Journals</source><source>Royal Society of Chemistry Journals Archive (1841-2007)</source><source>Alma/SFX Local Collection</source><creator>Clarke, Matthew L ; Ellis, Dianne ; Mason, Kate L ; Orpen, A Guy ; Pringle, Paul G ; Wingad, Richard L ; Zaher, Damien A ; Baker, R Tom</creator><creatorcontrib>Clarke, Matthew L ; Ellis, Dianne ; Mason, Kate L ; Orpen, A Guy ; Pringle, Paul G ; Wingad, Richard L ; Zaher, Damien A ; Baker, R Tom</creatorcontrib><description>The fluoroaryl phosphines P{C6H3(CF3)2-3,5}3 (La) and P(C6F5)3 (Lb) form the complexes trans-[MCl2(La)2] and trans-[MCl2(Lb)2](M = Pd or Pt) which have been isolated and fully characterised. 31P NMR studies of competition experiments show that the stability of trans-[PdCl2L2] is in the order L = Lb&lt; La &lt;PPh3. The crystal structure of trans-[PtCl2(La)2] is reported and reveals that the Pt-P bond lengths in trans-[PtCl2L2] are in the order L = Lb&lt; La &lt; PPh3. The equilibria established when [Pt(norbornene)3] is treated with or are investigated by 31P and 195Pt NMR spectroscopy and the species [PtLn(norbornene)3-n](n= 1-3) identified. Ligands and appear to have similar affinities for platinum(0). The complexes trans-[MCl(CO)(La)2] and trans-[MCl(CO)(Lb)2](M = Rh or Ir) have been synthesised and fully characterised; the values of nu(CO) are comparable with those for analogous phosphite complexes. The ligands La, Lb, P(C6H2F3-3,4,5)3 (Lc), P{C6H4(CF3)-2}3 (Ld), PPh3 and P(OPh)3 have been tested in rhodium-catalysed hydroformylation of 1-hexene and La, Lb, and PPh3 have been tested in rhodium-catalysed hydroformylation of 4-methoxystyrene. Ligands La, and Lb, have been shown to be stable under the hydroformylation catalysis conditions. For the 1-hexene reaction, the activity and selectivity for and are very similar to the PPh3 catalyst (TOF ca. 400 h(-1); n : iso 2.5-3.0) but for the sterically demanding and the activity and selectivity was much lower than with PPh3 (TOF ca. 15, n : iso ratio 0.6). Thus, the yield of heptanals obtained with the catalyst derived from La is 94% while under the same conditions with Lb only 6%. The TOF for the La/Rh catalyst was 5 times lower than for the P(OPh)3/Rh catalyst despite the superficially similar ligand electronic characteristics for La and P(OPh)3.</description><identifier>ISSN: 1477-9226</identifier><identifier>EISSN: 1477-9234</identifier><identifier>DOI: 10.1039/b418193j</identifier><identifier>PMID: 15782267</identifier><language>eng</language><publisher>England</publisher><ispartof>Dalton transactions : an international journal of inorganic chemistry, 2005-04 (7), p.1294-1300</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c146j-39dfae3466d85c3519cb8e3ddd5a1c54ee8aa651e4bb8e9120682c6395567a303</citedby><cites>FETCH-LOGICAL-c146j-39dfae3466d85c3519cb8e3ddd5a1c54ee8aa651e4bb8e9120682c6395567a303</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,2831,27924,27925</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/15782267$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Clarke, Matthew L</creatorcontrib><creatorcontrib>Ellis, Dianne</creatorcontrib><creatorcontrib>Mason, Kate L</creatorcontrib><creatorcontrib>Orpen, A Guy</creatorcontrib><creatorcontrib>Pringle, Paul G</creatorcontrib><creatorcontrib>Wingad, Richard L</creatorcontrib><creatorcontrib>Zaher, Damien A</creatorcontrib><creatorcontrib>Baker, R Tom</creatorcontrib><title>The electron-poor phosphines P{C6H3(CF3)2-3,5}3 and P(C6F5)3 do not mimic phosphites as ligands for hydroformylation. A comparison of the coordination chemistry of P{C6H3(CF3)2-3,5}3 and P(C6F5)3 and the unexpectedly low hydroformylation activity of their rhodium complexes</title><title>Dalton transactions : an international journal of inorganic chemistry</title><addtitle>Dalton Trans</addtitle><description>The fluoroaryl phosphines P{C6H3(CF3)2-3,5}3 (La) and P(C6F5)3 (Lb) form the complexes trans-[MCl2(La)2] and trans-[MCl2(Lb)2](M = Pd or Pt) which have been isolated and fully characterised. 31P NMR studies of competition experiments show that the stability of trans-[PdCl2L2] is in the order L = Lb&lt; La &lt;PPh3. The crystal structure of trans-[PtCl2(La)2] is reported and reveals that the Pt-P bond lengths in trans-[PtCl2L2] are in the order L = Lb&lt; La &lt; PPh3. The equilibria established when [Pt(norbornene)3] is treated with or are investigated by 31P and 195Pt NMR spectroscopy and the species [PtLn(norbornene)3-n](n= 1-3) identified. Ligands and appear to have similar affinities for platinum(0). The complexes trans-[MCl(CO)(La)2] and trans-[MCl(CO)(Lb)2](M = Rh or Ir) have been synthesised and fully characterised; the values of nu(CO) are comparable with those for analogous phosphite complexes. The ligands La, Lb, P(C6H2F3-3,4,5)3 (Lc), P{C6H4(CF3)-2}3 (Ld), PPh3 and P(OPh)3 have been tested in rhodium-catalysed hydroformylation of 1-hexene and La, Lb, and PPh3 have been tested in rhodium-catalysed hydroformylation of 4-methoxystyrene. Ligands La, and Lb, have been shown to be stable under the hydroformylation catalysis conditions. For the 1-hexene reaction, the activity and selectivity for and are very similar to the PPh3 catalyst (TOF ca. 400 h(-1); n : iso 2.5-3.0) but for the sterically demanding and the activity and selectivity was much lower than with PPh3 (TOF ca. 15, n : iso ratio 0.6). Thus, the yield of heptanals obtained with the catalyst derived from La is 94% while under the same conditions with Lb only 6%. The TOF for the La/Rh catalyst was 5 times lower than for the P(OPh)3/Rh catalyst despite the superficially similar ligand electronic characteristics for La and P(OPh)3.</description><issn>1477-9226</issn><issn>1477-9234</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2005</creationdate><recordtype>article</recordtype><recordid>eNqFUcFu1DAQDQhES0GCH0A-VVuJtLEdO8mxiliKVIke2nPktSfEK8cOtgONqv57ve0WDhw4eTzz5r03eln2ARenuKDN2abENW7o9mV2iMuqyhtCy1d_asIPsrchbIuCkIKRN9kBZlWd2tXhi4_XAyAwIKN3Np-c82gaXJgGbSGgq7uWX9BVu6YnJKef2T1Fwip0tWr5mp1QpByyLqJRj1o-78W0JwIy-keCBtQnxmFR3qViXIyI2tlTdI6kGyfhdXAWuR7F5EImcaXtIwLJAUYdol920__Z2H12DLOF2ymdAsosyLjf_wgjIaP-peOy19Qe-cEpPY-PfgzcQniXve6FCfB-_x5lN-sv1-1Ffvn967f2_DKXuOTbnDaqF0BLzlXNJGW4kZsaqFKKCSxZCVALwRmGcpP6DSYFr4nktGGMV4IW9Cg7fuKdvPs5Q4hdOliCMcKCm0PHK0aampEEXD0BpXcheOi7yetR-KXDRbeLv3uOP0E_7TnnzQjqL3CfN30ApgmrLQ</recordid><startdate>20050407</startdate><enddate>20050407</enddate><creator>Clarke, Matthew L</creator><creator>Ellis, Dianne</creator><creator>Mason, Kate L</creator><creator>Orpen, A Guy</creator><creator>Pringle, Paul G</creator><creator>Wingad, Richard L</creator><creator>Zaher, Damien A</creator><creator>Baker, R Tom</creator><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope></search><sort><creationdate>20050407</creationdate><title>The electron-poor phosphines P{C6H3(CF3)2-3,5}3 and P(C6F5)3 do not mimic phosphites as ligands for hydroformylation. A comparison of the coordination chemistry of P{C6H3(CF3)2-3,5}3 and P(C6F5)3 and the unexpectedly low hydroformylation activity of their rhodium complexes</title><author>Clarke, Matthew L ; Ellis, Dianne ; Mason, Kate L ; Orpen, A Guy ; Pringle, Paul G ; Wingad, Richard L ; Zaher, Damien A ; Baker, R Tom</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c146j-39dfae3466d85c3519cb8e3ddd5a1c54ee8aa651e4bb8e9120682c6395567a303</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2005</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Clarke, Matthew L</creatorcontrib><creatorcontrib>Ellis, Dianne</creatorcontrib><creatorcontrib>Mason, Kate L</creatorcontrib><creatorcontrib>Orpen, A Guy</creatorcontrib><creatorcontrib>Pringle, Paul G</creatorcontrib><creatorcontrib>Wingad, Richard L</creatorcontrib><creatorcontrib>Zaher, Damien A</creatorcontrib><creatorcontrib>Baker, R Tom</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Clarke, Matthew L</au><au>Ellis, Dianne</au><au>Mason, Kate L</au><au>Orpen, A Guy</au><au>Pringle, Paul G</au><au>Wingad, Richard L</au><au>Zaher, Damien A</au><au>Baker, R Tom</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>The electron-poor phosphines P{C6H3(CF3)2-3,5}3 and P(C6F5)3 do not mimic phosphites as ligands for hydroformylation. A comparison of the coordination chemistry of P{C6H3(CF3)2-3,5}3 and P(C6F5)3 and the unexpectedly low hydroformylation activity of their rhodium complexes</atitle><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle><addtitle>Dalton Trans</addtitle><date>2005-04-07</date><risdate>2005</risdate><issue>7</issue><spage>1294</spage><epage>1300</epage><pages>1294-1300</pages><issn>1477-9226</issn><eissn>1477-9234</eissn><abstract>The fluoroaryl phosphines P{C6H3(CF3)2-3,5}3 (La) and P(C6F5)3 (Lb) form the complexes trans-[MCl2(La)2] and trans-[MCl2(Lb)2](M = Pd or Pt) which have been isolated and fully characterised. 31P NMR studies of competition experiments show that the stability of trans-[PdCl2L2] is in the order L = Lb&lt; La &lt;PPh3. The crystal structure of trans-[PtCl2(La)2] is reported and reveals that the Pt-P bond lengths in trans-[PtCl2L2] are in the order L = Lb&lt; La &lt; PPh3. The equilibria established when [Pt(norbornene)3] is treated with or are investigated by 31P and 195Pt NMR spectroscopy and the species [PtLn(norbornene)3-n](n= 1-3) identified. Ligands and appear to have similar affinities for platinum(0). The complexes trans-[MCl(CO)(La)2] and trans-[MCl(CO)(Lb)2](M = Rh or Ir) have been synthesised and fully characterised; the values of nu(CO) are comparable with those for analogous phosphite complexes. The ligands La, Lb, P(C6H2F3-3,4,5)3 (Lc), P{C6H4(CF3)-2}3 (Ld), PPh3 and P(OPh)3 have been tested in rhodium-catalysed hydroformylation of 1-hexene and La, Lb, and PPh3 have been tested in rhodium-catalysed hydroformylation of 4-methoxystyrene. Ligands La, and Lb, have been shown to be stable under the hydroformylation catalysis conditions. For the 1-hexene reaction, the activity and selectivity for and are very similar to the PPh3 catalyst (TOF ca. 400 h(-1); n : iso 2.5-3.0) but for the sterically demanding and the activity and selectivity was much lower than with PPh3 (TOF ca. 15, n : iso ratio 0.6). Thus, the yield of heptanals obtained with the catalyst derived from La is 94% while under the same conditions with Lb only 6%. The TOF for the La/Rh catalyst was 5 times lower than for the P(OPh)3/Rh catalyst despite the superficially similar ligand electronic characteristics for La and P(OPh)3.</abstract><cop>England</cop><pmid>15782267</pmid><doi>10.1039/b418193j</doi><tpages>7</tpages></addata></record>
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source Royal Society Of Chemistry Journals; Royal Society of Chemistry Journals Archive (1841-2007); Alma/SFX Local Collection
title The electron-poor phosphines P{C6H3(CF3)2-3,5}3 and P(C6F5)3 do not mimic phosphites as ligands for hydroformylation. A comparison of the coordination chemistry of P{C6H3(CF3)2-3,5}3 and P(C6F5)3 and the unexpectedly low hydroformylation activity of their rhodium complexes
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