- Synthesis of phosphiranes
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Phosphiranes, three-membered phosphorus-containing heterocycles, have been prepared via reaction of tertiary phosphines dilithium derivatives with carbon tetrachloride. The elaborated method can be applied for preparation of some phosphiranes which are not easily accessible.
- Kolodyazhnaya,Kolodyazhnyi
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p. 436 - 440
(2015/04/14)
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- Synthesis of Anti-Cis-Phosphiranes
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A method for the preparation of three-membered phosphoric heterocycles-phosphi-ranes by reaction of dilithium derivatives of tertiary phosphines with tetrachloromethane is described. The reaction is stereoselective and leads to the formation of anti-cis(meso)-2,3-diphenylphosphiranes. Phosphiranes were isolated as individual compounds and their structure was confirmed by 1H, 13C, and 31P NMR spectra, and mass spectra. The present method is simple and can be successfully used for the preparation of some types of phosphiranes that are inaccessible by other methods.
- Kolodiazhna, Olga O.,Kolodiazhnyi, Oleg I.
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p. 1192 - 1200
(2015/08/04)
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- Synthesis, characterization and reactivity of tribenzylphosphine rhodium and iridium complexes
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New rhodium and iridium complexes, with the formula [MCl(PBz 3)(cod)] [M = Rh (1), Ir (2)] and [M(PBz3) 2(cod)]PF6 [M = Rh (3), Ir (4)] (cod = 1,5-cyclooctadiene), stabilized by the tribenzylphosphine ligand (PBz 3) were synthesized and characterized by elemental analysis and spectroscopic methods. The molecular structures of 1 and 2 were determined by single-crystal X-ray diffraction. The addition of pyridine to a methanol solution of 1or 2, followed by metathetical reaction with NH4PF 6, gave the corresponding derivatives [M(py)(PBz3)(cod)] PF6 [M = Rh (5), Ir (6)]. At room temperature in CHCl3 solution, 4 converted spontaneously to the ortho-metallated complex [IrH(PBz3)(cod){η2-P,C-(C6H 4CH2)PBz2}]PF6 (7) as a mixture of cis/trans isomers via intramolecular C-H activation of a benzylic phenyl ring. The reaction of 3 or 4 with hydrogen in coordinating solvents gave the dihydrido bis(solvento) derivative [M(H)2(S)2(PBz3) 2]PF6 (M = Rh, Ir; S = acetone, acetonitrile, THF), that transformed into the corresponding dicarbonyls [M(H)2(CO) 2(PBz3)2]PF6 by treatment with CO. Analogous cis-dihydrido complexes [M(H)2(THF)2(py) (PBz3)2]PF6 (M = Rh, Ir) were observed by reaction of the py derivatives 5 and 6 with H2.
- Landaeta, Vanessa R.,Peruzzini, Maurizio,Herrera, Verónica,Bianchini, Claudio,Sánchez-Delgado, Roberto A.,Goeta, Andrés E.,Zanobini, Fabrizio
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p. 1039 - 1050
(2007/10/03)
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- Hydrogenolysis process
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A process of hydrogenolysis utilizing a new catalyst consisting of a palladium phosphine complex, the phosphien having a pKa greater than or equal to 6, a chlorinated aromatic compound and hydrogen.
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- Low pressure rhodium catalyzed hydroformylation of olefins
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The hydroformylation of olefins with rhodium complex catalysts is described. The catalysts employed comprise a rhodium complex with at least one phosphine having a specified structure, e.g., tris(benzyl)phosphine. Preferred phosphines have a pKa in the range of about 3.5 up to 5.3 and a cone angle in the range of about 160 up to 195°. Hydroformylation reactions at relatively low temperatures and pressure and yet with high rates of reaction and high selectivity to aldehyde product are obtained by the practice of the present invention.
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- Selective formation of ethanol from methanol, hydrogen and carbon monoxide
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A process for the selective formation of ethanol which comprises contacting methanol, hydrogen and carbon monoxide with a catalyst system comprising cobalt acetylacetonate, a tertiary organo Group V A compound of the periodic Table, a first promoter comprising an iodine compound and a second promoter comprising a ruthenium compound.
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- Process for tris(aralkyl)phosphines
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In a solution that is free of bases and free of oxygen and which contains at least four molar proportions of the reactant tris(hydroxymethyl)phosphine for every three molar proportions of an aralkyl halide reactant, the following reaction produces tris(aralkyl)phosphine product: after separation of the phosphine product, the phosphonium salt by-products can be converted to tris(hydroxymethyl)phosphine by the addition of a base.
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