Hypervalent, Low-Coordinate Phosphorus(III) Centers in Complexes of the Phosphadiazonium Cation with Chelate Ligands
Trifluoromethylsulfonyloxy-(2,4,6-tri-tert-butylphenylimino)phosphine, Mes*NPOTf (Mes* = 2,4,6-tri-tert-butylphenyl, OTf = trifluoromethanesulfonate, triflate) reacts quantitatively with the multifunctional ligands 2,2‘-bipyridine (2,2‘-BIPY), N,N,N‘,N‘-tetramethylethylenediamine (TMEDA), 1,2-bis(di...
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| Veröffentlicht in: | Journal of the American Chemical Society 2005-03, Vol.127 (11), p.3921-3927 |
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| container_title | Journal of the American Chemical Society |
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| creator | Burford, Neil Phillips, Andrew D Spinney, Heather A Lumsden, Michael Werner-Zwanziger, Ulrike Ferguson, Michael J McDonald, Robert |
| description | Trifluoromethylsulfonyloxy-(2,4,6-tri-tert-butylphenylimino)phosphine, Mes*NPOTf (Mes* = 2,4,6-tri-tert-butylphenyl, OTf = trifluoromethanesulfonate, triflate) reacts quantitatively with the multifunctional ligands 2,2‘-bipyridine (2,2‘-BIPY), N,N,N‘,N‘-tetramethylethylenediamine (TMEDA), 1,2-bis(diethylphosphino)ethane (DEPE), 1,2-bis(diphenylphosphino)ethane (DIPHOS), and N,N,N‘,N‘ ‘,N‘ ‘-pentamethyldiethylenetriamine (PMDETA) to give the Lewis acid−base complexes [Mes*NP(2,2‘-BIPY)][OTf], [Mes*NP(TMEDA)][OTf], [Mes*NP(DIPHOS)][OTf], [Mes*NP(DEPE)][OTf], and [Mes*NP(PMDETA)][OTf], respectively. Single-crystal X-ray diffraction studies indicate that the closest contact of the ligand donor atoms occurs at phosphorus in all cases, affecting significant displacement of the OTf anion. The resulting cations [Mes*NP(L)]+ are best described as complexes of a neutral chelating ligand on a phosphadiazonium Lewis acceptor, and highlight the potential for electron-rich centers to behave as Lewis acids despite the presence of a lone pair of electrons at the acceptor site. More importantly, the new complexes represent rare examples of systems containing hypervalent, low-coordinate phosphorus(III) centers. |
| doi_str_mv | 10.1021/ja043691y |
| format | Article |
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Single-crystal X-ray diffraction studies indicate that the closest contact of the ligand donor atoms occurs at phosphorus in all cases, affecting significant displacement of the OTf anion. The resulting cations [Mes*NP(L)]+ are best described as complexes of a neutral chelating ligand on a phosphadiazonium Lewis acceptor, and highlight the potential for electron-rich centers to behave as Lewis acids despite the presence of a lone pair of electrons at the acceptor site. More importantly, the new complexes represent rare examples of systems containing hypervalent, low-coordinate phosphorus(III) centers.</description><identifier>ISSN: 0002-7863</identifier><identifier>EISSN: 1520-5126</identifier><identifier>DOI: 10.1021/ja043691y</identifier><identifier>PMID: 15771528</identifier><identifier>CODEN: JACSAT</identifier><language>eng</language><publisher>Washington, DC: American Chemical Society</publisher><subject>Chemistry ; Exact sciences and technology ; Organic chemistry</subject><ispartof>Journal of the American Chemical Society, 2005-03, Vol.127 (11), p.3921-3927</ispartof><rights>Copyright © 2005 American Chemical Society</rights><rights>2005 INIST-CNRS</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a381t-c8f4a3eac804f64bab0828f59d137645d28cf8656e7e6686c0ccdadf1bc1cfa23</citedby><cites>FETCH-LOGICAL-a381t-c8f4a3eac804f64bab0828f59d137645d28cf8656e7e6686c0ccdadf1bc1cfa23</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/ja043691y$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/ja043691y$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,776,780,2751,27055,27903,27904,56716,56766</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=16635220$$DView record in Pascal Francis$$Hfree_for_read</backlink><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/15771528$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Burford, Neil</creatorcontrib><creatorcontrib>Phillips, Andrew D</creatorcontrib><creatorcontrib>Spinney, Heather A</creatorcontrib><creatorcontrib>Lumsden, Michael</creatorcontrib><creatorcontrib>Werner-Zwanziger, Ulrike</creatorcontrib><creatorcontrib>Ferguson, Michael J</creatorcontrib><creatorcontrib>McDonald, Robert</creatorcontrib><title>Hypervalent, Low-Coordinate Phosphorus(III) Centers in Complexes of the Phosphadiazonium Cation with Chelate Ligands</title><title>Journal of the American Chemical Society</title><addtitle>J. Am. Chem. Soc</addtitle><description>Trifluoromethylsulfonyloxy-(2,4,6-tri-tert-butylphenylimino)phosphine, Mes*NPOTf (Mes* = 2,4,6-tri-tert-butylphenyl, OTf = trifluoromethanesulfonate, triflate) reacts quantitatively with the multifunctional ligands 2,2‘-bipyridine (2,2‘-BIPY), N,N,N‘,N‘-tetramethylethylenediamine (TMEDA), 1,2-bis(diethylphosphino)ethane (DEPE), 1,2-bis(diphenylphosphino)ethane (DIPHOS), and N,N,N‘,N‘ ‘,N‘ ‘-pentamethyldiethylenetriamine (PMDETA) to give the Lewis acid−base complexes [Mes*NP(2,2‘-BIPY)][OTf], [Mes*NP(TMEDA)][OTf], [Mes*NP(DIPHOS)][OTf], [Mes*NP(DEPE)][OTf], and [Mes*NP(PMDETA)][OTf], respectively. Single-crystal X-ray diffraction studies indicate that the closest contact of the ligand donor atoms occurs at phosphorus in all cases, affecting significant displacement of the OTf anion. The resulting cations [Mes*NP(L)]+ are best described as complexes of a neutral chelating ligand on a phosphadiazonium Lewis acceptor, and highlight the potential for electron-rich centers to behave as Lewis acids despite the presence of a lone pair of electrons at the acceptor site. More importantly, the new complexes represent rare examples of systems containing hypervalent, low-coordinate phosphorus(III) centers.</description><subject>Chemistry</subject><subject>Exact sciences and technology</subject><subject>Organic chemistry</subject><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2005</creationdate><recordtype>article</recordtype><recordid>eNpt0MFu1DAQBmALgehSOPACyBcQlQjYTuK4R4goXWkRlSiImzXr2MRLYqe2Q7s8PV7t0r1wGo3m06_Rj9BzSt5Swui7DZCq5Od0-wAtaM1IUVPGH6IFIYQVjeDlCXoS4yavFRP0MTqhddNkKBYoXW4nHX7DoF16g1f-tmi9D511kDS-6n2ceh_m-Hq5XJ7hNiMdIrYOt36cBn2nI_YGp_6fhc7CH-_sPOIWkvUO39rU47bXwy5wZX-C6-JT9MjAEPWzwzxF3y4-XreXxerLp2X7flVAKWgqlDAVlBqUIJXh1RrWRDBh6vOOlg2v6o4JZQSvuW4054IrolQHnaFrRZUBVp6iV_vcKfibWcckRxuVHgZw2s9R8iaXJcgOnu2hCj7GoI2cgh0hbCUlclexvK842xeH0Hk96u4oD51m8PIAICoYTACnbDw6zsuaMZJdsXc2Jn13f4fwKz9WNrW8vvoqP1QXP-rmcym_H3NBRbnxc3C5u_88-Bct_6AR</recordid><startdate>20050323</startdate><enddate>20050323</enddate><creator>Burford, Neil</creator><creator>Phillips, Andrew D</creator><creator>Spinney, Heather A</creator><creator>Lumsden, Michael</creator><creator>Werner-Zwanziger, Ulrike</creator><creator>Ferguson, Michael J</creator><creator>McDonald, Robert</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>IQODW</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope></search><sort><creationdate>20050323</creationdate><title>Hypervalent, Low-Coordinate Phosphorus(III) Centers in Complexes of the Phosphadiazonium Cation with Chelate Ligands</title><author>Burford, Neil ; Phillips, Andrew D ; Spinney, Heather A ; Lumsden, Michael ; Werner-Zwanziger, Ulrike ; Ferguson, Michael J ; McDonald, Robert</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a381t-c8f4a3eac804f64bab0828f59d137645d28cf8656e7e6686c0ccdadf1bc1cfa23</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2005</creationdate><topic>Chemistry</topic><topic>Exact sciences and technology</topic><topic>Organic chemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Burford, Neil</creatorcontrib><creatorcontrib>Phillips, Andrew D</creatorcontrib><creatorcontrib>Spinney, Heather A</creatorcontrib><creatorcontrib>Lumsden, Michael</creatorcontrib><creatorcontrib>Werner-Zwanziger, Ulrike</creatorcontrib><creatorcontrib>Ferguson, Michael J</creatorcontrib><creatorcontrib>McDonald, Robert</creatorcontrib><collection>Istex</collection><collection>Pascal-Francis</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Journal of the American Chemical Society</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Burford, Neil</au><au>Phillips, Andrew D</au><au>Spinney, Heather A</au><au>Lumsden, Michael</au><au>Werner-Zwanziger, Ulrike</au><au>Ferguson, Michael J</au><au>McDonald, Robert</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Hypervalent, Low-Coordinate Phosphorus(III) Centers in Complexes of the Phosphadiazonium Cation with Chelate Ligands</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>2005-03-23</date><risdate>2005</risdate><volume>127</volume><issue>11</issue><spage>3921</spage><epage>3927</epage><pages>3921-3927</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><coden>JACSAT</coden><abstract>Trifluoromethylsulfonyloxy-(2,4,6-tri-tert-butylphenylimino)phosphine, Mes*NPOTf (Mes* = 2,4,6-tri-tert-butylphenyl, OTf = trifluoromethanesulfonate, triflate) reacts quantitatively with the multifunctional ligands 2,2‘-bipyridine (2,2‘-BIPY), N,N,N‘,N‘-tetramethylethylenediamine (TMEDA), 1,2-bis(diethylphosphino)ethane (DEPE), 1,2-bis(diphenylphosphino)ethane (DIPHOS), and N,N,N‘,N‘ ‘,N‘ ‘-pentamethyldiethylenetriamine (PMDETA) to give the Lewis acid−base complexes [Mes*NP(2,2‘-BIPY)][OTf], [Mes*NP(TMEDA)][OTf], [Mes*NP(DIPHOS)][OTf], [Mes*NP(DEPE)][OTf], and [Mes*NP(PMDETA)][OTf], respectively. Single-crystal X-ray diffraction studies indicate that the closest contact of the ligand donor atoms occurs at phosphorus in all cases, affecting significant displacement of the OTf anion. The resulting cations [Mes*NP(L)]+ are best described as complexes of a neutral chelating ligand on a phosphadiazonium Lewis acceptor, and highlight the potential for electron-rich centers to behave as Lewis acids despite the presence of a lone pair of electrons at the acceptor site. More importantly, the new complexes represent rare examples of systems containing hypervalent, low-coordinate phosphorus(III) centers.</abstract><cop>Washington, DC</cop><pub>American Chemical Society</pub><pmid>15771528</pmid><doi>10.1021/ja043691y</doi><tpages>7</tpages></addata></record> |
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| title | Hypervalent, Low-Coordinate Phosphorus(III) Centers in Complexes of the Phosphadiazonium Cation with Chelate Ligands |
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