- Arylation of red phosphorus: A new way to triphenylphosphine oxide and triphenylphosphine
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Nickel bromide catalyses the arylation of amorphous red phosphorus. This provides a new way to triphenylphosphine oxide and triphenylphosphine.
- Cristau, Henri-Jean,Pascal, Jeanick,Plenat, Francoise
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- A simple and efficient phosphorescent probe for iodide-specific detection based on crystallization-induced phosphorescence of organic ionic crystals
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It is very challenging to develop luminescent detection methods for iodide ions due to their significant fluorescence quenching of general fluorophores induced by the heavy-atom effect. Herein, we reveal a unique crystallization-induced bright phosphorescence of tetraphenylphosphonium iodide (TPP I) and develop a novel time-gated detection method for iodide ions to minimize the autofluorescence from complex biological samples. Both the involvement of heavy iodide ion and accessible ionic interaction-induced organic crystals contribute to the accomplishment of a very high phosphorescence quantum yield (0.42) for TPP I. This specific iodide-triggered bright organic phosphorescence enables the development of a novel time-gated detection method for iodide ions in the luminescence turn-on manner and further offers an opportunity to establish a facile test strip for the visual detection of iodide ions based on solid-state phosphorescence on a solid substrate. Excellent performance of this probe in imaging iodide in live cells and intriguing use in double encryption illustrate the versatile and broad application prospects of highly efficient organic ionic crystals in various areas.
- Chen, Guilin,Zhou, Jin,Feng, Hui,Feng, Feifei,Xu, Pengfei,Pan, Saifei,Xu, Jing,Qian, Zhaosheng
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- A comparative electrochemical study on corrosion inhibition of iron by synthesized tetraphenyl phosphonuim iodide in acid media
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The present work is aimed mainly to synthesize a phosphonuim salt, tetraphenylphosphonuim iodide, and evaluate inhibitive effect against carbon steel corrosion in aerated 1 M HCl solutions. Thus, tetraphenylphosphonuim iodide was synthesized by the reaction of of an equimolar quantity of a solution of phenyl iodide and triphenyl phosphine in toluene (84% yield). We have found that, the use of toluene for this reaction of triphenyl phosphine with aryl or alkyl iodide is a convenient synthesis of many phosphonium salts since the halogen as a leaving group (requires a temperature higher than boiling point of chloroform.The purity of this compound was estimated by TLC technique and microanalysis, while its structure was supported by the usual spectroscopic methods such as UV, infrared, 1H. NMR and 13C. NMR. Exploration of the Corrosion measurements based on polarization resistance (Rp), potentiodynamic polarization curves indicates that tetraphenylphosphonuim iodide, in most cases act as strong inhibitors. Tetraphenylphosphonuim iodide acts as anodic type inhibitors with predominant effect on the anodic dissolution of iron. Analysis of the polarization curves indicates that charge transfer process mainly controls carbon steel corrosion in HCl solution without and with phosphonuim salt. The mechanism of corrosion inhibition by phosphonuim; salt was discussed in the light of the molecular structure of the additive. A Comparative electrochemical study with that reported in the literature revealed that the efficiency of the inhibitors follows the order: tetraphenyl phosphonum iodide >(chloromethyl) triphenyl phosphonium chloride (CTP) > tetraphenyl phosphonum chloride (TP) > triphenyl phosphine oxide (TPO) > triphenyl (phenylmethyl) phosphonium chloride (TPM).
- Mansouri, Khaled,Sekhri, Lakhdar,Rahim, Oumelkheir,Tabchouche, Ahmed
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- Photocatalytic Arylation of P4 and PH3: Reaction Development Through Mechanistic Insight
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Detailed 31P{1H} NMR spectroscopic investigations provide deeper insight into the complex, multi-step mechanisms involved in the recently reported photocatalytic arylation of white phosphorus (P4). Specifically, these studies have identified a number of previously unrecognized side products, which arise from an unexpected non-innocent behavior of the commonly employed terminal reductant Et3N. The different rate of formation of these products explains discrepancies in the performance of the two most effective catalysts, [Ir(dtbbpy)(ppy)2][PF6] (dtbbpy=4,4′-di-tert-butyl-2,2′-bipyridine) and 3DPAFIPN. Inspired by the observation of PH3 as a minor intermediate, we have developed the first catalytic procedure for the arylation of this key industrial compound. Similar to P4 arylation, this method affords valuable triarylphosphines or tetraarylphosphonium salts depending on the steric profile of the aryl substituents.
- Cammarata, Jose,Gschwind, Ruth M.,Lennert, Ulrich,Rothfelder, Robin,Scott, Daniel J.,Streitferdt, Verena,Wolf, Robert,Zeitler, Kirsten
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supporting information
p. 24650 - 24658
(2021/10/14)
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- Chalcogen-Bonding Catalysis with Telluronium Cations
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Chalcogen bonding results from non-covalent interactions occurring between electrodeficient chalcogen atoms and Lewis bases. Among the chalcogens, tellurium is the strongest Lewis acid, but Te-based compounds are scarcely used as organocatalysts. For the first time, telluronium cations demonstrated impressive catalytic properties at low loadings in three benchmark reactions: the Friedel–Crafts bromination of anisole, the bromolactonization of ω-unsaturated carboxylic acids and the aza-Diels–Alder between Danishefsky's diene and imines. The ability of telluronium cations to interact with a Lewis base through chalcogen bonding was demonstrated on the basis of multi-nuclear (17O, 31P, and 125Te) NMR analysis and DFT calculations.
- Aubert, Emmanuel,Mamane, Victor,Pale, Patrick,Weiss, Robin
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supporting information
p. 19281 - 19286
(2021/07/25)
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- Continuous synthesis method of tetraphenylphosphinophenylphenol salt
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The method uses triphenylphosphine, halogenated benzene and phenol as raw materials, and the sodium hydroxide solution is an acid binding agent. The preparation method comprises the following steps: triphenylphosphine. The halogenated benzene and the reaction solvent are mixed in a continuous flow reactor to prepare a tetraphenylhalogenated phosphine solution, a prepared tetraphenylhalogenated phosphine solution, phenol and sodium hydroxide solution with a concentration 32% are mixed in a continuous flow reactor to prepare a tetraphenylphosphine phenol salt. Compared with a conventional stirred tank reactor, the reactor used in the preparation method is smaller in size, simple to operate, continuous in reaction, high in yield, environmentally friendly, stable in pH value during reaction, relatively mild in reaction conditions and stable in prepared tetraphenylphenol salt.
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Paragraph 0022; 0035-0036
(2021/09/01)
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- Versatile Visible-Light-Driven Synthesis of Asymmetrical Phosphines and Phosphonium Salts
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Asymmetrically substituted tertiary phosphines and quaternary phosphonium salts are used extensively in applications throughout industry and academia. Despite their significance, classical methods to synthesize such compounds often demand either harsh reaction conditions, prefunctionalization of starting materials, highly sensitive organometallic reagents, or expensive transition-metal catalysts. Mild, practical methods thus remain elusive, despite being of great current interest. Herein, we describe a visible-light-driven method to form these products from secondary and primary phosphines. Using an inexpensive organic photocatalyst and blue-light irradiation, arylphosphines can be both alkylated and arylated using commercially available organohalides. In addition, the same organocatalyst can be used to transform white phosphorus (P4) directly into symmetrical aryl phosphines and phosphonium salts in a single reaction step, which has previously only been possible using precious metal catalysis.
- Arockiam, Percia Beatrice,Lennert, Ulrich,Graf, Christina,Rothfelder, Robin,Scott, Daniel J.,Fischer, Tillmann G.,Zeitler, Kirsten,Wolf, Robert
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supporting information
p. 16374 - 16382
(2020/11/03)
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- Preparation, structure, and reactivity of dipalladium(I) complexes containing the carbanion 2-C6F4PPh2: Coexistence of distinct, noninterconverting head-to-head [dipalladium(0/II)] and head-to-tail [dipalladium(I)] species
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Comproportionation of trans-[Pd(κ2-2-C6F 4PPh2)2] with [PdL4] (L = PPh 3, AsPh3) gives metal-metal-bonded dipalladium(I) complexes [Pd2I(μ-2-C6F4PPh 2)2(L)2] [L = PPh3 (5), AsPh 3 (6)] in which the bridging ligands adopt a head-to-tail arrangement. The corresponding diplatinum(I) complex [Pt2 I(μ-2-C6F4PPh2) 2(PPh3)2] (9) is obtained similarly from [Pt(κ2-2-C6F4PPh2) 2] and [Pt(PPh3)3]. The separations between the metal atoms in the dipalladium(I) complexes [2.5740(3) A (5), 2.5511(3) A (6)] are slightly less than that in the diplatinum(I) complex 9 [2.61179(15) A]. The axial triphenylarsine ligands of 6 are replaced by tert-butyl isocyanide to give the dipalladium(I) complex [Pd2 I(μ-2-C6F4PPh2) 2(CNtBu)2] (7). However, treatment of trans-[Pd(κ2-2-C6F4PPh2) 2] with [Pd(CNtBu)2], generated in situ from a mixture of tert-butyl isocyanide and [Pd(η5-Cp) (η3-allyl)], gives a formally mixed-valent palladium(0)- palladium(II) complex [Pd20/II(μ-2-C6F 4PPh2)2(CNtBu)2] (8), in which the bridging ligands are arranged head-to-head. In contrast, comproportionation of [Pt(κ2-2-C6F 4PPh2)2] with [Pt3(CN tBu)6] gives the diplatinum(I) complex [Pt 2I(μ-2-C6F4PPh2) 2(CNtBu)2] (10) analogous to 7; there was no evidence for the formation of a dinuclear mixed-valent species. Although complexes 7 and 8 are isomers, with similar Pd-Pd separations [2.5803(4) A (7), 2.5580(2) A (8)], they do not interconvert in solution. The diplatinum(I) complex 9 undergoes oxidative addition with iodine to give an A-frame cation, [Pt2(μ-I)(μ-2-C6F 4PPh2)2(PPh3)2] +, isolated as its PF6- salt (11). In contrast, the dipalladium(I) complex 5 eliminates one of the PPh3 ligands when it undergoes oxidative addition with halogens and with methyl iodide, the products being A-frame dipalladium(II) complexes [Pd2X(μ-Y)(μ- 2-C6F4PPh2)2(PPh3)] [X = Y = I (12), Cl (13); X = Me, Y = I (14)]. The metal-metal distances in 11-14 [2.9478(5) A (11), 2.8078(7) A (12), 2.8241(3) A (13), and 2.8013(5) A (14)] are ca. 0.3 A greater than in their dimetal(I) precursors, consistent with a weaker metal-metal interaction in the dimetal(II) complexes. Unexpectedly, reaction of 5 with iodobenzene gives a mononuclear palladium(II) complex, cis-[Pd(κ2C,P-2-C6F 4PPh2)(κC-2-C6F4PPh 2)(PPh3)] (15). This is suggested to be formed by a sequence of (a) oxidative addition of iodobenzene to 5 to give a σ-phenyl complex analogous to the σ-methyl complex 14, (b) a change in the binding mode of one of the 2-C6F4PPh2 ligands from μ- to κ2-, and (c) reductive elimination of tetraphenylphosphonium iodide and loss of Pd(0).
- Bhargava, Suresh K.,Priver, Steven H.,Willis, Anthony C.,Bennett, Martin A.
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p. 5561 - 5572,12
(2020/08/31)
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- Palladium-catalyzed synthesis of functionalized tetraarylphosphonium salts
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(Chemical Equation Presented) An efficient method to synthesize functionalized tetraarylphosphonium salts is described. This palladium-catalyzed coupling reaction between aryl iodides, bromides, or triflates and triphenylphosphine generates phosphonium salts in high yields. The coupling is compatible with a variety of functional groups such as alcohols, ketones, aldehydes, phenols, and amides.
- Marcoux, David,Charette, Andre B.
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p. 590 - 593
(2008/09/17)
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- Thermal stability, decomposition paths, and Ph/Ph exchange reactions of [(Ph3P)2Pd(Ph)X] (X = I, Br, Cl, F, and HF2)
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Complexes of the type [(Ph3P)2Pd(Ph)X], where X = I (1), Br (2), Cl (3), F (4), and HF2 (5), possess different thermal stability and reactivity toward the Pd-Ph/P-Ph exchange reactions. While 1 decomposed (16 h) in toluene at 110 °C to [Ph4P]I, Pd metal, and Ph3P, complexes 2 and 3 exhibited no sign of decomposition under these conditions. Kinetic studies of the aryl-aryl exchange reactions of [(Ph3P)2Pd(C6D5)X] in benzene-de demonstrated that the rate of exchange decreases in the order 1 > 2 > 3, the observed rate constant ratio, kI:kBr:kCl, in benzene at 75 °C being ca. 100:4:1 for 1-d5, 2-d5, and 3-d5. The exchange was facilitated by a decrease in the concentration of the complex, polar media, and a Lewis acid, e.g., Et2O·BF3. Unlike [Bu4N]PF6, which speeded up the exchange reaction of 2-d5, [Bu4N]-Br inhibited it due to the formation of anionic four-coordinate [(Ph3P)Pd(C6D5)Br2]-. The latter and its iodo analogue were generated in dichloromethane and benzene upon addition of [Bu4N]X or PPN Cl to [(Ph3P)2Pd2(Ph)2(μ-X) 2] (X = I, Br, or Cl) and characterized in solution by 1H and 31P NMR spectral data. The mechanism of the aryl-aryl exchange reactions of [(Ph3P)2Pd(C6D5)X] in noncoordinating solvents of low polarity may not require Pd-X ionization but rather involves phosphine dissociation, the ease of which decreases in the order X = I > Br > Cl, as suggested by crystallographic data. Two mechanisms govern the thermal reactions of [(Ph3P)2Pd(Ph)F], 4. One of them is similar to the aryl-aryl exchange and decomposition path for 1-3, involving a tight ion pair intermediate, [Ph4P][(Ph3P)PdF], within which two processes were shown to occur. At 75 °C, the C-P oxidative addition restores the original neutral complex (4). At 90 °C, reversible fluoride transfer from Pd to the phosphonium cation resulted in the formation of covalent [Ph4PF] and [(Ph3P)Pd], which was trapped by PhI to produce [(Ph3P)2Pd2(Ph)2(μ-I) 2]. The other decomposition path of 4 leads to the formation of [(Ph3P)3Pd], Pd, Ph2 , Ph3PF2, and Ph2P-PPh2 as main products. Unlike the aryl-aryl exchange, this decomposition reaction is not inhibited by free phosphine. The formation of biphenyl was shown to occur due to PdPh/PPh coupling on the metal center. Mechanisms accounting for the formation of these products are proposed and discussed. The facile (4 h at 75 °C) thermal decomposition of [(Ph3P)2Pd(Ph)(FHF)] (5) in benzene resulted in the clean formation of PhH, Ph3PF2, Pd metal, and [(Ph3P)3Pd].
- Grushin, Vladimir V.
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p. 1888 - 1900
(2008/10/08)
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- Coordination Catalysis in Organic Electrosynthesis. Electrochemical Phosphorylation of Organic Halides in the Presence of Samarium Dichloride
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The feasibility was demonstrated for arylation (or alkylation) of white phosphorus under the action of electrochemically generated Sm(II).
- Budnikova,Yakhvarov,Kargin
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p. 566 - 569
(2007/10/03)
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- MODIFIED SYNTHESIS METHODS AND PHYSICOCHEMICAL STUDY OF AZIDOPHOSPHORANES AS MATERIALS FOR PHOTORESISTS-DIFFUSANTS
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Azidophosphorane derivative have been proposed as light-sensitive and doping components of photoresists-diffusants.Methods for their synthesis have been developed and improved, and the main physicochemical and phototechnical characteristics of these compounds in solutions and in cyclohexanone polymer matrices have been determined.
- Galai, B. O.,Busygina, L. A.,Yurre, T. A.
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p. 1751 - 1754
(2007/10/03)
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- 13C and 31P NMR Studies of Some Aminophosphonium Chlorides
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The multinuclear NMR spectral data for an homologous series of tertiary phosphines R(3-n)P(NMe2)(n), aminophosphonium ions, (+), and phosphonium ions, (+), where R=Me, Et, (n)-Pr and Ph, R' and/or R''=H, Me and n=0 and 1 are reported and discussed.Quaternization by alkylation or alkylation or chloramination causes an increase in the 31P chemical shift (ΔδP is positive), a decrease in the 13C chemical shift (ΔδC is negative) for all carbons, an increase in the magnitudes of 1J(PC), 3J(PC), 3J(PNCH) and 2J(PCH) and a decrease in the magnitude of 2J(PC).Substitution of a Me2N group for an alkyl or aryl group produces an increase in the 31P chemical shift and in the magnitude of 1J(PC). α- and β-deshielding and γ-shielding effects are noted in the 13C NMR spectra and β-deshielding and γ-shielding effects are noted in the 31P NMR spectra with substitution on the phosphorus and nitrogen atoms. - Key words: 13C NMR, 31P NMR, Tertiary phosphines, Aminophosphonium ions, Phosphonium ions
- Krannich, Larry K.,Kanjolia, Ravindra K.,Watkins, Charles L.
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p. 320 - 324
(2007/10/02)
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- Convenient Preparation of Tetraarylphosphonium Halides
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Tetraarylphosphonium halides, particularly iodides, can be conveniently prepared by the Pd-catalyzed reaction of aryl halides and triarylphosphines in good yields.
- Migita, Toshihiko,Nagai, Tohru,Kiuchi, Kazuhiko,Kosugi, Masanori
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p. 2869 - 2870
(2007/10/02)
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