Rhodium Complexes of Sterically Demanding Diphosphonites: Coordination Chemistry and Catalysis
The coordination chemistry of various sterically constrained diphosphonites 1−6 with rhodium are reported. The stoichiometric reaction of ligand 5 with [Rh(μ-Cl(CO)2]2 gives rise to the sole formation of trans-[RhCl(CO)(5)] (7), as shown by NMR and IR spectroscopy and X-ray crystallography. The mole...
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Veröffentlicht in: | Organometallics 2004-06, Vol.23 (13), p.3177-3183 |
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description | The coordination chemistry of various sterically constrained diphosphonites 1−6 with rhodium are reported. The stoichiometric reaction of ligand 5 with [Rh(μ-Cl(CO)2]2 gives rise to the sole formation of trans-[RhCl(CO)(5)] (7), as shown by NMR and IR spectroscopy and X-ray crystallography. The molecular structure reveals a weak interaction between the metal center and the oxygen from the xanthene backbone. This complex serves as a structural model for the first intermediate in the catalytic cycle of rhodium hydroformylation, [Rh(H)(CO)(P⌒P)]. A detailed study on the solution structure of the catalyst resting state under catalytic conditions is performed by high-pressure NMR and FT-IR spectroscopy. The spectroscopic data show that under hydroformylation conditions the bidentate ligands form well-defined complexes with the structure [Rh(H)(CO)2(P⌒P)]. All ligands show preference for a bis-equatorial (ee) coordination mode in the trigonal-bipyramidal Rh complexes. These novel sterically constrained diphosphonite ligands are applied in the rhodium hydroformylation of 1-octene and 2-butene, and good activities and regioselectivities are obtained. |
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M. M ; Mills, Allison M ; Spek, Anthony L ; Vogt, Dieter</creator><creatorcontrib>van der Vlugt, Jarl Ivar ; Sablong, Rafaël ; Magusin, Pieter C. M. M ; Mills, Allison M ; Spek, Anthony L ; Vogt, Dieter</creatorcontrib><description>The coordination chemistry of various sterically constrained diphosphonites 1−6 with rhodium are reported. The stoichiometric reaction of ligand 5 with [Rh(μ-Cl(CO)2]2 gives rise to the sole formation of trans-[RhCl(CO)(5)] (7), as shown by NMR and IR spectroscopy and X-ray crystallography. The molecular structure reveals a weak interaction between the metal center and the oxygen from the xanthene backbone. This complex serves as a structural model for the first intermediate in the catalytic cycle of rhodium hydroformylation, [Rh(H)(CO)(P⌒P)]. A detailed study on the solution structure of the catalyst resting state under catalytic conditions is performed by high-pressure NMR and FT-IR spectroscopy. The spectroscopic data show that under hydroformylation conditions the bidentate ligands form well-defined complexes with the structure [Rh(H)(CO)2(P⌒P)]. All ligands show preference for a bis-equatorial (ee) coordination mode in the trigonal-bipyramidal Rh complexes. 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A detailed study on the solution structure of the catalyst resting state under catalytic conditions is performed by high-pressure NMR and FT-IR spectroscopy. The spectroscopic data show that under hydroformylation conditions the bidentate ligands form well-defined complexes with the structure [Rh(H)(CO)2(P⌒P)]. All ligands show preference for a bis-equatorial (ee) coordination mode in the trigonal-bipyramidal Rh complexes. These novel sterically constrained diphosphonite ligands are applied in the rhodium hydroformylation of 1-octene and 2-butene, and good activities and regioselectivities are obtained.</description><issn>0276-7333</issn><issn>1520-6041</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2004</creationdate><recordtype>article</recordtype><recordid>eNptkL1OwzAUhS0EEqUw8AZeGBgCdlzbMRuk_EmVKG2ZLdd2qEsSV3YqtRsrr8mTYFTUieHqDvc7R_ccAM4xusIox9e-QQNRFEIcgB6mOcoYGuBD0EM5ZxknhByDkxiXCCHGSd4DarLwxq0bWPpmVduNjdBXcNrZ4LSq6y0c2ka1xrXvcOhWCx_TtK6z8eb78yuJfEg31TnfwnJhGxe7sIVJAEvVqXobXTwFR5Wqoz37233w9nA_K5-y0cvjc3k7yhQhqMswQ6yihhKqhRFqrglFFdaFKgxXms4pNkRzwgUyoiCGF2bA5rktkoBhayvSB5c7Xx18jMFWchVco8JWYiR_u5H7bhKb7dj0r93sQRU-ZKqFUzkbT-X4lQ3F5K6UNPEXO17pKJd-HdqU5B_fH3ENdCI</recordid><startdate>20040621</startdate><enddate>20040621</enddate><creator>van der Vlugt, Jarl Ivar</creator><creator>Sablong, Rafaël</creator><creator>Magusin, Pieter C. M. 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M</au><au>Mills, Allison M</au><au>Spek, Anthony L</au><au>Vogt, Dieter</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Rhodium Complexes of Sterically Demanding Diphosphonites: Coordination Chemistry and Catalysis</atitle><jtitle>Organometallics</jtitle><addtitle>Organometallics</addtitle><date>2004-06-21</date><risdate>2004</risdate><volume>23</volume><issue>13</issue><spage>3177</spage><epage>3183</epage><pages>3177-3183</pages><issn>0276-7333</issn><eissn>1520-6041</eissn><abstract>The coordination chemistry of various sterically constrained diphosphonites 1−6 with rhodium are reported. The stoichiometric reaction of ligand 5 with [Rh(μ-Cl(CO)2]2 gives rise to the sole formation of trans-[RhCl(CO)(5)] (7), as shown by NMR and IR spectroscopy and X-ray crystallography. The molecular structure reveals a weak interaction between the metal center and the oxygen from the xanthene backbone. This complex serves as a structural model for the first intermediate in the catalytic cycle of rhodium hydroformylation, [Rh(H)(CO)(P⌒P)]. A detailed study on the solution structure of the catalyst resting state under catalytic conditions is performed by high-pressure NMR and FT-IR spectroscopy. The spectroscopic data show that under hydroformylation conditions the bidentate ligands form well-defined complexes with the structure [Rh(H)(CO)2(P⌒P)]. All ligands show preference for a bis-equatorial (ee) coordination mode in the trigonal-bipyramidal Rh complexes. These novel sterically constrained diphosphonite ligands are applied in the rhodium hydroformylation of 1-octene and 2-butene, and good activities and regioselectivities are obtained.</abstract><pub>American Chemical Society</pub><doi>10.1021/om0498899</doi><tpages>7</tpages><oa>free_for_read</oa></addata></record> |
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title | Rhodium Complexes of Sterically Demanding Diphosphonites: Coordination Chemistry and Catalysis |
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