- One-pot synthesis of magnetic iron phosphide nanoparticles
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A novel one-pot synthetic method to produce crystalline tri-octylphosphine (TOP) capped iron phosphide nanoparticles is reported here. Standard method of synthesizing FeP includes preparation of a precursor, sodium phosphide, which is finally reacted with ferric chloride (FeCl3).The methods for synthesizing iron phosphide (FeP), reported so far, rely on the use of toxic red or yellow phosphorus to generate the precursor, Sodium phosphide (Na3P). In present investigation, instead of red or yellow phosphorus, a relatively less toxic substance TOP and sodium metal (Na) have been used to yield Na3P. The synthesized nanoparticles were fully characterized by X-ray diffraction pattern (XRD), Infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS), Transmission electron microscopy (TEM) and superconducting quantum interference device (SQUID) analyses. The results showed that the synthesized FeP nanoparticles have the characteristic orthorhombic crystal structures, with the size ~10 nm and the coercivity 70 Oe at RT.
- Ahluwalia, Deepali,Varshney, Atul,Kumar, Sachin,Kumar, Anil,Warkar, Sudhir Gopalrao,Singh, Narendra,Dubey, Prashant
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- NASICON SOLID ELECTROLYTES. PART IV. CHEMICAL DURABILITY.
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The chemical durability of NASICON (Na//1// plus //xZr//2Si//xP//3// minus //xO//1//2, x equals 0-3) versus molten sodium and sulfur at 600 K has been investigated. Degradation by molten sodium has been observed for phosphorus-containing compositions only
- Kreuer,Warhus
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- A solvothermal synthesis of ultra-fine iron phosphide
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Powder iron phosphide (FeP) has been prepared via a benzene-thermal synthesis with the reaction of anhydrous iron chloride (FeCl3) and sodium phosphide (Na3P) at 180-190°C. The product was analyzed by X-ray photoelectron spectroscopy (XPS), and the results show the mole ratio of Fe:P is 1.12. X-ray diffraction (XRD) pattern can be indexed to the orthorhombic cell of FeP with the lattice constant a = 5.191, b = 3.101, and c = 5.789 A?. Transmission electron microscope (TEM) images indicate that average particle size is about 200nm in diameter.
- Yunle, Gu,Fan, Guo,Yitai, Qian,Huagui, Zheng,Ziping, Yang
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- On the Crystal Structure and Conductivity of Na3P
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As a potential material for Na-ion battery systems and on the basis of a structural discussion of compounds formerly believed to crystallize in the so-called Na3As type the structure of Na3P has been reinvestigated. Na3P is found to crystallize in the Cu3P type, analogous to Na3As and is described by a three times larger unit cell [P63cm, a = 8.61224(10) ? and c = 8.81949(10) ?] compared to the former model [P63/mmc, a = 4.9512(5) ? and c = 8.7874(13) ?]. As a structural manifestation of this symmetry reduction corrugated layers of Na and P atoms are observed which had formerly to be described as planar. The high purity of the material further enables the determination of its properties, showing mainly semiconducting behavior with a conductivity of 12 S·cm–1 at room temperature.
- Eickhoff, Henrik,Dietrich, Christian,Klein, Wilhelm,Zeier, Wolfgang. G.,F?ssler, Thomas F.
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- Exploration of Novel α,ω-Substituted Diphosphatrisilanes by Combining Experimental Methods and DFT Calculations
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The novel diphosphatrisilanes {(R2P-Si(SiMe3)2-)2-SiMe2} [R = Ph, H] and the cyclophosphatrisilabutanes {R–PSi3} [R = H, SiMe3] have been prepared via salt metathesis reactions between phosphanides and 2,4-dihalogenated pentasilanes and characterized via NMR spectroscopy. The experimental results were supported by DFT calculations. Although P–Si bond formation was observed in all cases, the outcome of the reactions varied depending on the nature of ligands on the phosphanides, forming either linear diphosphatrisilanes or cyclic phosphatrisilacyclobutanes. DFT studies were performed to get a better understanding of the reactions. The precursor silanes were fully characterized using NMR spectroscopy and single-crystal X-ray diffraction and offer interesting building blocks. In addition, a modified route for the synthesis of P(TMS)3 was successfully carried out, achieving high yields of up to 73 %, circumventing the use of white phosphorus and phosphine gas during the reaction.
- Weinberger, Gernot P.,Sommer, Florian,Torvisco, Ana,Fischer, Roland C.,Flock, Michaela
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- Solvothermal preparation of tin phosphide nanorods
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Tin phosphide nanorods were successfully obtained through a mild and simple solvothermal route. The synthesis was performed through the solvothermal process based on metathesis reaction between SnCl2 and Na3P at 120-140 °C. Reaction conditions including solvent, temperature, and the valence state of raw materials thin salts were important factors to the morphology, crystallization, and purity of nanocrystalline Sn4P3.
- Xie, Yi,Su, Huilan,Li, Bin,Qian, Yitai
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- Phospha derivatives of Tris(2-aminoethyl)amine (tren) and tris(3-aminopropyl)amine (trpn): Synthesis and complexation studies with group 4 metals
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The N,N′,N-triphenyl-substituted derivative of tris(2-aminoethyl)phosphine (Ph3-phospha-tren, P(CH2CH2NHR)3, R = Ph) and four derivatives of the related tris(3-aminopropyl)phosphine (phospha-trpn, P(CH2CH2CH2NHR)3, R = iPr, tBu, SitBuMe2, Ph) have been synthesized in addition to the parent phospha-trpn. Out of these ligand systems, only the N,N′,N-triphenyl-substituted phospha-trpn derivative P(CH2CH2CH2NHPh)3 was found to be suitable for coordination to group 4 metals. For titanium, zirconium, and hafnium, the C3-symmetric endo-P-configured dimethylamido complexes Ph[PN3]M(NMe2) of the former ligand have been prepared and converted into the corresponding triflates Ph[PN3]M(OTf). Starting from these triflates, the benzyl complexes Ph[PN3]M(Bn) (M = Ti, Zr, Hf) have been obtained via reaction with Bn2Mg(THF)2. In case of titanium, the benzyl species Ph[PN3]Ti(Bn) is prone to thermal elimination of toluene, which results in the formation of a cyclometalated species. These findings are discussed in context with the very few group 4 trisamidophosphine complexes that have been reported earlier.
- Sietzen, Malte,Batke, Sonja,Merz, Lukas,Wadepohl, Hubert,Ballmann, Joachim
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- Synthesis, Structure and Reactivity of a Cyapho-Cyanamide Salt
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We describe a facile synthesis of the cyapho-cyanamide salt [Na(18-crown-6)][N(CN)(CP)] from reaction of [Na(18-crown-6)][PH2] (18-crown-6=1,4,7,10,13,16-hexaoxacyclooctadecane) with dimethyl N-cyanocarbonimidate, (MeO)2C=N(CN). The reaction proceeds with elimination of two equivalents of methanol. Careful tuning of the reaction conditions allowed for the isolation and characterization of the N-cyano(carboximidate)phosphide intermediate [HP{C(OMe)N(CN)}]?. Due to the adverse effects of methanol in these reaction mixtures, a bulk scale synthesis of [Na(18-crown-6)][N(CN)(CP)] could be achieved by addition of a base (LiHMDS) to neutralize the resulting alcohol. Further reactivity studies of this anion reveal that functionalization at the phosphorus atom is viable to yield a new family of cyanide-functionalised phosphorus heterocycles.
- Erg??men, Doruk,Goicoechea, Jose M.
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supporting information
p. 25286 - 25289
(2021/10/25)
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- Electrochemical Oxidation of the Phospha- and Arsaethynolate Anions, PCO– and AsCO–
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The anions PCO– and AsCO– are shown to be electroactive and are studied in aqueous and non-aqueous solutions. Cyclic voltammetry is used to extract fundamental physicochemical parameters such as oxidation peak potentials, and transfer and diffusion coefficients of the anions to better understand the nature of the oxidation process. Variation of the potential scan rate reveals that electro-oxidation of PCO– with the release of CO is controlled by diffusion and is a one-electron irreversible process yielding phosphorus-containing deposits. In contrast, the oxidation of AsCO– is a near electrochemically reversible process, forming pure arsenic deposits, with a chemically irreversible follow-up reaction. For both anions, the electrode surface is substantially “blocked” by the reaction products. The formed deposits were characterized by scanning electron microscopy and energy dispersive X-ray spectroscopy.
- Tambornino, Frank,Tanner, Eden E. L.,Amin, Hatem M. A.,Holter, Jennifer,Claridge, Tim,Compton, Richard G.,Goicoechea, Jose M.
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p. 1644 - 1649
(2019/01/29)
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- DERIVATIVES OF BISACYLPHOSPHINIC ACID, THEIR PREPARATION AND USE AS PHOTOINITIATORS
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Bisacylphosphine oxide or bisacylphosphine sulfide compounds of formula (I) or (II) wherein R1, R2, R3, R1a, R2a and R3a independently of each other are C1-C4alkyl, C1-C4alkoxy or halogen; X is O, NR5 or S; or, if R4 is CI, F or Br, X is a direct bond; Y is O or S; n is 1 or 2; R4, if n is 1, for example is hydrogen, (CO)R6, (CO)OR6, (CO)NR5R6, (SO2)-R6, C1-C28alkyl, R4, if n = 2, is for example C1-C18alkylene; R5 is for example hydrogen, or C1-C12alkyl; R6 is for example C1-C12alkyl; R7, R8 and R9 independently of each other for example are C1-C4alkyl; R10 is for example C2-C18alkylene; X1 is O or S; m is 1, 2 or 3; Q represents one or two inorganic or organic cations with a charge of m+; are suitable photoinitiators, available by a claimed process.
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Page/Page column 72
(2014/07/08)
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- Preparation of secondary phosphines
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The present invention relates to a method for preparing di-α-chiral and achiral di(sec. alkyl)phosphines of general formula Ia or Ib which is characterized in that sulfonates of general formula IIa or IIc or sulfates of general formula IIb or IId, are rea
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(2010/11/29)
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- PROCESS FOR PREPARING ACYLPHOSPHANES AND DERIVATIVES THEREOF
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The invention relates to a process for the preparation of (bis)acylphosphanes of formula I, wherein n and m are each independently of the other 1 or 2; R1 if n = 1 , is e.g. unsubstituted or substituted C1-C18alkyl or C2-C18alkenyl, or phenyl, R1 if n = 2, is e.g. a divalent radical of the monovalent radical defined above; R2 is e.g. C1-C18alkyl, C3-C12cycloalkyl, C2-C18alkenyl, mesityl, phenyl, naphthyl; R3 is one of the radicals defined under R1; the process comprises the steps a) contacting e.g. elemental phosphorous [P]∞, P(Hal)3 with a reducing metal optionally in the presence of a catalyst or an activator in a solvent to obtain metal phosphides Me3P or Me'3P2, wherein Me is an alkali metal and Me' is an earth alkali metal or to obtain metal polyphosphides b) optionally adding a proton source, optionally in the presence of a catalyst or an activator to obtain metal dihydrogen phosphides MePH2; c) subsequent acylation reaction with m acid halides of formula III or m carboxylic acid esters of formula IV or, in case that in formula I m = 1, with one carboxylic ester of formula IV followed by one acid halide of formula III or vice versa, wherein R is the residue of an alcohol and R2 is as defined above; d) alkylation reaction subsequent reaction with an electrophilic agent R1Hal or other electrophilic agents to obtain the compounds of formula I. An oxidation step may follow to obtain mono- and bisacylphosphane oxides or mono- and bisacylphosphane sulfides, which are used as photoinitiators.
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(2010/11/08)
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- Self-propagating metathesis routes to metastable group 4 phosphides
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Group 4 phosphides, which are typically prepared at high temperatures (>800 °C) over several days, are synthesized in self-propagating metathesis (exchange) reactions in seconds. These reactions produce cubic forms of zirconium phosphide (ZrP) and hafnium phosphide (HfP) which are normally made at temperatures greater than 1425 °C and 1600 °C, respectively. To test whether the high temperatures reached in the metathesis reactions are responsible for the formation of the cubic phases, inert salts are added to lower the maximum reaction temperatures. The lower temperature reactions still result in cubic phosphides, although smaller crystallites form. Further experiments with phosphorus addition indicate that the phosphorus content is not responsible for cubic phase formation. Templating is ruled out using lattice mismatched KCl and hexagonal ZnS as additives. Therefore, the direct synthesis of the high-temperature cubic phase in metathesis reactions appears to be caused by nucleation of the metastable cubic form that is then trapped by rapid cooling. Heating the cubic phase of either ZrP or HfP to 1000 °C for 18 h, or carrying out metathesis reactions in sealed ampules at 1000 °C, results only in the hexagonal phase.
- Jarvis Jr., Robert F.,Jacubinas, Richard M.,Kaner, Richard B.
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p. 3243 - 3246
(2008/10/08)
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