- Phosphanyl Methanimine (PCN) Ligands for the Selective Trimerization/Tetramerization of Ethylene with Chromium
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1-Phosphanyl methanimine ligands, R2P-C(Ph)=NR′, may be prepared via a modular, convergent synthesis in good overall yield. Coordination chemistry studies with chromium confirm that they bind in a bidentate κ2-P,N mode. In combination with chromium and an activator, these ligands promote the selective oligomerization of ethylene to 1-hexene and 1-octene with high activity. Notably, an exceptionally high liquid fraction selectivity to saleable products (1-hexene + 1-octene) is observed (>95%), along with a potent ligand dependence, such that selectivity can be varied from pure trimerization through to mixed trimerisation/tetramerisation with a 1-octene:1-hexene (OTH) ratio of 1.7.
- Radcliffe, James E.,Batsanov, Andrei S.,Smith, David M.,Scott, John A.,Dyer, Philip W.,Hanton, Martin J.
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Read Online
- Synthetic method for bidentate phosphine
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The invention relates to a synthetic method for bidentate phosphine. The synthetic method comprises the following steps: in the protective atmosphere, using molten metal of sodium and potassium as a catalyst, using chlorodiphenylphosphine and trimethylchlorosilane as raw materials, using tetrahydrofuran as a solvent and reacting to obtain diphenyl(trimethylsilyl) phosphine; then reacting dichloromaleic anhydride with trialpyridine-substituted aniline to obtain a product, and continuously reacting the product with the diphenyl(trimethylsilyl) phosphine to obtain a target product. The synthetic method disclosed by the invention has the advantages of high yield, good purity, reduced cost and short reaction time.
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Paragraph 0012; 0026; 0030; 0034
(2017/11/18)
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- Preparation of diphenyl phosphide and substituted phosphines using alkali metal in silica gel (M-SG)
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Alkali metals absorbed in silica gel (the M-SG reagents) efficiently cleave C-P bonds in triaryl- and diarylphosphines. The resulting alkali metal phosphides can serve as useful building blocks for a variety of phosphines. Alkyldiarylphosphines undergo exclusive aryl group cleavage.
- Nandi, Partha,Dye, James L.,Bentley, Philip,Jackson, James E.
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supporting information; experimental part
p. 1688 - 1692
(2009/09/06)
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- A generic route to fluoroalkyl-containing phosphanes
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The reaction of trimethylsilyl-containing phosphanes with perfluoroiodoalkanes provides a general and convenient route to perfluoroalkyl-containing phosphanes. The Royal Society of Chemistry 2009.
- Brisdon, Alan K.,Herbert, Christopher J.
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supporting information; experimental part
p. 6658 - 6660
(2010/04/01)
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- Selective syntheses of mono- and diphosphanyltriazines as novel ligands for transition metal catalysts
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1,3,5-Triazines bearing one, two or three diphenylphosphanyl group(s) were selectively synthesized from cyanuric chloride by the one-pot step-by-step addition of silylphosphane and other nucleophiles. Mono- and diphosphanyltriazines with a variety of substituents on the triazine ring could be easily prepared in good yields. The Pd complexes of mono- and diphosphanyltriazine were isolated, and the crys-tal structures were determined. Polymer-supported and water-soluble ligands were prepared. The Mizorogi-Heckreaction and the Suzuki-Miyaura coupling reaction using the phosphanyltriazine-Pd catalysts are described.
- Hayashi, Minoru,Yamasaki, Toshikazu,Kobayashi, Yusuke,Imai, Yoshito,Watanabe, Yutaka
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experimental part
p. 4956 - 4962
(2010/02/27)
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- METHOD FOR GENERATING ALKALI METAL PHOSPHIDES THROUGH REDUCTION OF TRI-SUBSTITUTED PHOSPHINES WITH ALKALI METAL POROUS OXIDE COMPOSITIONS
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Alkali metal phosphides are useful intermediates for the synthesis of a variety of phosphine derivatives. Many of these phosphine derivatives are important industrial compounds with applications as synthetic intermediates or as ligands in a variety of homogeneous and heterogeneous synthetic processes. Alkali metal diarylphosphides in particular have been used in the synthesis of many phosphine ligands of importance. The invention relates to methods for generating and using alkali metal phosphides by reduction of the phosphorus sigma bonds of tri-substituted phosphorus derivatives with Group I metal/porous oxide compositions. Formula (I).
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Page/Page column 18-19
(2008/12/08)
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- Fluorescence enhancement by hydroperoxides based on a change in the intramolecular charge transfer character of benzofurazan
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Strong fluorescence signals were observed after the reaction of novel reagents with hydroperoxides. The Royal Society of Chemistry 2005.
- Onoda, Maki,Tokuyama, Hidetoshi,Uchiyama, Seiichi,Mawatari, Ken-Ichi,Santa, Tomofumi,Kaneko, Kiyoko,Imai, Kazuhiro,Nakagomi, Kazuya
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p. 1848 - 1850
(2007/10/03)
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- P/O ligand systems: Facile synthesis, structure, and catalytic tests of 2′-phosphanyl-1,1′-bipheny 1-2-ols and 2′-phosphanyl-1,1′-binaphthyl-2-ols
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A facile synthesis of 2′-phosphanyl-1,1′-biphenyl- and 2′-phosphanyl-l,1′-binaphthyl-2-ols and their silyl ethers has been developed, consisting of electron-transfer-catalyzed ring-opening of dibenzofuran and dinaphthofuran, respectively, subsequent reaction with chlorophosphanes, and work-up with acetic acid or ClSiMe3. Studies of the molecular and crystal structures reveal the presence of P...H-O bridging bonds in the more basic /BuPhP derivative and a nearly perpendicular arrangement of the aryl planes in the biphenyl derivatives. The barrier to rotation of the aryl planes about the C-C axis was determined by NMR in the case of the P-asymmetric derivative 3d, using the appearance of diastereoisomers by atropisomerism and P-asymmetry. Comparative screening tests of the title compounds, phosphanylphenols and phosphanylnaphthols in homogeneous Rh-catalyzed reactions demonstrate catalytic activity in hydroformylation reactions and superior properties of the biphenyl- and binaphthyl-2-ol derivatives in relation to other P-O ligands. WILEY-VCH Verlag GmbH, 1997.
- Kadyrov, Renat,Heinicke, Joachim,Kindermann, Markus K.,Heller, Detlef,Fischer, Christine,Selke, Ruediger,Fischer, Axel K.,Jones, Peter G.
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p. 1663 - 1670
(2007/10/03)
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- ZUR REAKTION VON PHOSPHORVERBINDUNGEN MIT SCHWESINGER BASEN-I P-C-BINDUNGKNUEPFUNG AN P-H-FUNKTIONELLEN PHOSPHORVERBINDUNGEN
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Secondary and tertiary phosphines (RR'PH; R2R'P) may be synthesized by alkylation of primary or secondary phosphines with organo halides (R' = Et, n-C7H15, Bz, Me3Si; X = Cl, Br) in the presence of Schwesinger bases as auxillary bases in high yields.Alkylation of diphenylphosphine with alkylene dihalides and Schwesinger bases affords alkylendiphosphines. Key words: Alkylation; secondary and tertiary phosphines; Schwesinger bases.
- Uhlig, Frank,Puschner, Beatrix,Herrmann, Eckhard,Zobel, Bernhard,Bernhardt, Henry,Uhlig, Wolfram
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p. 155 - 164
(2007/10/02)
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- Palladium-Catalyzed Coupling of Aryl Halides with (Trimethylstannyl)diphenylphosphine and (Trimethylsilyl)diphenylphosphine
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The palladium-catalyzed reaction of aryl halides with either (trimethylsilyl)diphenylphosphine or (trimethylstannyl)diphenylphosphine gives aryldiphenylphosphines in good yields, under relatively mild conditions (50-70 deg C, benzene).The reaction tolerates a number of functional groups including methyl ethers, esters, ketones, nitriles, anilides, and certain halogens.The nitro and aldehyde groups as well as compounds containing groups such as amino and hydroxyl are not tolerated.
- Tunney, S. E.,Stille, J. K.
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p. 748 - 753
(2007/10/02)
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- DIE REAKTION VON ALKALIPHOSPHIDEN MIT WEISSEM PHOSPHOR, I1 BILDUNG VON 1,1,3,3-TETRAPHENYL-TRIPHOSPHID, 2,3,4,5-TETRAPHENYL-CYCLOPENTAPHOSPHID UND PHENYL-TRICYCLOHEPTAPHOSPHID
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The redox reactions between p4 and alkali metal phosphides in THF are followed by 31P NMR spectroscopy.As reduction products polyphosphides, mainly M3P7 (3) are formed.The activation energy of the valence tautomerism of 3 is somewhat lower for M = Na than for M = Li.As oxidation products MPh2P give the triphosphides MPh4P3 (1) and the diphosphane Ph4P2 (2); M2(PhP)n, N = 1,2,3 extend their chain up to n = 4; K2(PhP)4 yields the cyclopentaphosphide KPh4P5 (6), Li2PhP the tricycloheptaphosphide Li2PhP7 (7).
- Schmidpeter, Alfred,Burget, Guenther
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p. 323 - 336
(2007/10/02)
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