554-70-1Relevant articles and documents
Phosphine-substituted and phosphido-bridged metal clusters in homogeneous catalysis I. Synthesis and reactivity of (η5-C5H5)NiM3(μ-H)3(CO)(9-n)Ln (M = Ru, Os, n = 1,2: L = PPh3, PPh2H, PCy3, PEt3) and M3(CO)(12-n)Ln (M = Ru, N = 1-3: L = PPh3,
Castiglioni, Mario,Giordano, Roberto,Sappa, Enrico
, p. 97 - 110 (1988)
The complexes (η5-C5H5)NiM3(μ-H)3(CO)(9-n)Ln (M = Ru, Os, n = 1.2: L = PPh3, PPh2H, PCy3, PEt3) and M3(CO)(12-n)Ln (M = Ru, n = 1-3: L = PPh3, PPh2H, PCy3, PEt3; M = Os, n = 1,2: L = PPh3) have been synthesized by new or known procedures.Reacti
Bis(pertrifluoromethylcatecholato)silane: Extreme Lewis Acidity Broadens the Catalytic Portfolio of Silicon
Thorwart, Thadd?us,Roth, Daniel,Greb, Lutz
supporting information, p. 10422 - 10427 (2021/05/27)
Given its earth abundance, silicon is ideal for constructing Lewis acids of use in catalysis or materials science. Neutral silanes were limited to moderate Lewis acidity, until halogenated catecholato ligands provoked a significant boost. However, catalytic applications of bis(perhalocatecholato)silanes were suffering from very poor solubility and unknown deactivation pathways. In this work, the novel per(trifluoromethyl)catechol, H2catCF3, and adducts of its silicon complex Si(catCF3)2 (1) are described. According to the computed fluoride ion affinity, 1 ranks among the strongest neutral Lewis acids currently accessible in the condensed phase. The improved robustness and affinity of 1 enable deoxygenations of aldehydes, ketones, amides, or phosphine oxides, and a carbonyl-olefin metathesis. All those transformations have never been catalyzed by a neutral silane. Attempts to obtain donor-free 1 attest to the extreme Lewis acidity by stabilizing adducts with even the weakest donors, such as benzophenone or hexaethyl disiloxane.
The Trityl-Cation Mediated Phosphine Oxides Reduction
Landais, Yannick,Laye, Claire,Lusseau, Jonathan,Robert, Frédéric
supporting information, p. 3035 - 3043 (2021/05/10)
Reduction of phosphine oxides into the corresponding phosphines using PhSiH3 as a reducing agent and Ph3C+[B(C6F5)4]? as an initiator is described. The process is highly efficient, reducing a broad range of secondary and tertiary alkyl and arylphosphines, bearing various functional groups in generally good yields. The reaction is believed to proceed through the generation of a silyl cation, which reaction with the phosphine oxide provides a phosphonium salt, further reduced by the silane to afford the desired phosphine along with siloxanes. (Figure presented.).
Reversing Lewis acidity from bismuth to antimony
Balasubramaniam, Selvakumar,Jemmis, Eluvathingal D.,Kumar, Sandeep,Sharma, Deepti,Venugopal, Ajay
supporting information, p. 8889 - 8892 (2021/09/10)
Investigations on the boundaries between the neutral and cationic models of (Mesityl)2EX (E = Sb, Bi and X = Cl?, OTf?) have facilitated reversing the Lewis acidity from bismuth to antimony. We use this concept to demonstrate a higher efficiency of (Mesityl)2SbOTf(Mesityl)2BiOTf in the catalytic reduction of phosphine oxides to phosphines. The experiments supported with computations described herein will find use in designing new Lewis acids relevant to catalysis.
Method for producing alkyl phosphine
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Paragraph 0044-0059, (2020/11/23)
The invention provides a method for producing alkyl phosphine, and specifically relates to a method for producing triethyl phosphine. The method comprises the following steps: mixing hydrogen phosphide with ethylene in a solvent, adding a photocatalyst, and carrying out a reaction for 1-12 h under illumination of 20-50 W to obtain triethyl phosphine, wherein the reaction temperature being 0-50 DEGC. According to the invention, under an illumination condition, the photocatalyst easily induces a radical reaction to enhance the reaction activity of hydrogen phosphide and olefin so as to substantially improve the reaction efficiency, the rapid reaction can be performed at the room temperature and the normal pressure, the reaction time is short, the pollution and the toxicity of the catalyst are low, the toxicity of the used solvent is low compared to the toxicity of toluene and the like commonly used in the prior art, the post-treatment is relatively simple, and the yield and the purity of the product are high.
A Universally Applicable Methodology for the Gram-Scale Synthesis of Primary, Secondary, and Tertiary Phosphines
Rinehart, N. Ian,Kendall, Alexander J.,Tyler, David R.
supporting information, p. 182 - 190 (2018/02/06)
Although organophosphine syntheses have been known for the better part of a century, the synthesis of phosphines still represents an arduous task for even veteran synthetic chemists. Phosphines as a class of compounds vary greatly in their air sensitivity, and the misconception that it is trivial or even easy for a novice chemist to attempt a seemingly straightforward synthesis can have disastrous results. To simplify the task, we have previously developed a methodology that uses benchtop intermediates to access a wide variety of phosphine oxides (an immediate precursor to phosphines). This synthetic approach saves the air-free handling until the last step (reduction to and isolation of the phosphine). Presented herein is a complete general procedure for the facile reduction of phosphonates, phosphinates, and phosphine oxides to primary, secondary, and tertiary phosphines using aluminum hydride reducing agents. The electrophilic reducing agents (iBu)2AlH and AlH3 were determined to be vastly superior to LiAlH4 for reduction selectivity and reactivity. Notably, it was determined that AlH3 is capable of reducing the exceptionally resistant tricyclohexylphosphine oxide, even though LiAlH4 and (iBu)2AlH were not. Using this new procedure, gram-scale reactions to synthesize a representative range of primary, secondary, and tertiary phosphines (including volatile phosphines) were achieved reproducibly with excellent yields and unmatched purity without the need for a purification step.
Organocatalyzed Reduction of Tertiary Phosphine Oxides
Schirmer, Marie-Luis,Jopp, Stefan,Holz, Jens,Spannenberg, Anke,Werner, Thomas
supporting information, p. 26 - 29 (2016/01/25)
A novel selective catalytic reduction method of tertiary phosphine oxides to the corresponding phosphines has been developed. Notably, the reaction proceeds smoothly with low catalyst loadings of 1-5 mol% even at low temperature (70 C). Under the optimized conditions various phosphine oxides could be selectively reduced and the desired phosphines were usually obtained in excellent yields above 90%. Furthermore, we have developed a one-pot reaction sequence for the preparation of valuable phosphinborane adducts. Simple addition of BH3THF subsequent to the reduction step gave the desired adducts in yields up to 99%.
Synthetic method for triethylphosphine
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Paragraph 0014; 0015, (2016/10/10)
The invention discloses a synthetic method for triethylphosphine and belongs to the field of preparation of compounds. The synthetic method comprises the steps that firstly, under the protection of nitrogen, chloroethane and magnesium chips react in a xylene and tetrahydrofuran mixed solvent with methyl iodide as an initiating agent to obtain ethylmagnesium chloride; secondly, a product obtained in the first step does not need to be purified, is directly added with phosphorus trichloride after being cooled, reacts at a low temperature through stirring and is directly subjected to decompression distillation after the reaction is finished, and a triethylphosphine product with the purity higher than 99% is obtained, and the yield reaches 89.9%. The solvent used in the synthetic method is easy to recycle.
Synthesis of a rhodium(i) germyl complex: A useful tool for C-H and C-F bond activation reactions
Ahrens, Theresia,Ahrens, Mike,Braun, Thomas,Braun, Beatrice,Herrmann, Roy
, p. 4716 - 4728 (2016/03/19)
The dihydrido germyl complex cis,fac-[Rh(GePh3)(H)2(PEt3)3] (2) was synthesized by an oxidative addition of HGePh3 at [Rh(H)(PEt3)3] (1). Treatment of 2 with neohexene generated the rhodium(i) germyl complex [Rh(GePh3)(PEt3)3] (3). Alternatively, treatment of the methyl complex [Rh(CH3)(PEt3)3] (4) with HGePh3 furnished at room temperature also 3. Low-temperature NMR measurements revealed an initial formation of the oxidative addition product fac-[Rh(GePh3)(H)(CH3)(PEt3)3] (5), which transforms into the intermediate complex [Rh(GePh3)(H)(CH3)(PEt3)2] (6) by dissociation of a triethylphosphine ligand. The reductive elimination of methane and coordination of PEt3 afforded the germyl complex 3. Treatment of 3 with CO gave the biscarbonyl complex [Rh(GePh3)(CO)2(PEt3)2] (7). The molecular structures of the complexes 2, 3 and 7 were determined by X-ray crystallography. The germyl complex 3 reacted with 2,3,5,6-tetrafluoropyridine or pentafluorobenzene to furnish the C-H activation products [Rh(4-C5NF4)(PEt3)3] (8) and [Rh(C6F5)(PEt3)3] (9), respectively. The reaction of 3 with hexafluorobenzene or perfluorotoluene gave selectively the C-F activation products 9 and [Rh(4-C6F4CF3)(PEt3)3] (10). Treatment of 3 with pentafluoropyridine resulted in the formation of the C-F activation products 8 and [Rh(2-C5NF4)(PEt3)3] (11) in a 1 : 10 ratio. The two isomeric activation compounds [Rh{(E)-CF=CF(CF3)}(PEt3)3] (12) and [Rh{(Z)-CF=CF(CF3)}(PEt3)3] (13) were obtained in a 3 : 1 ratio by reaction of 3 with hexafluoropropene. On exposure to oxygen the highly air sensitive complex 12 reacts to yield the peroxido-bridged dirhodium complex [Rh{(E)-CF=CF(CF3)}(μ-κ1:η2-O2)(PEt3)2]2 (14). The molecular structure of 14 was determined by X-ray crystallography.
NOVEL FLUORINATED ALKYLFLUOROPHOSPHORIC ACID SALT OF ONIUM AND TRANSITION METAL COMPLEX
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Page/Page column 19-20, (2010/11/25)
[Problems] To obtain a polymerization initiator (acid generating agent) having excellent power for initiation of cationic polymerization without containing arsenic or antimony. [Means for solution] Provided is a specific onium salt or transition metal complex salt of a fluorinated alkyl fluorophosphoric acid.
