- Kinetics of phosphine hydroxymethylation with formaldehyde
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The kinetics of phosphine hydroxymethylation with formaldehyde is studied. In the absence of a catalyst, phosphine reacts slowly with formaldehyde under normal conditions. Taken separately, amines, hydrochloric acid, and nickel chloride have a low catalytic activity, but the addition of a primary aliphatic amine to nickel chloride effectively increases the hydroxymethylation rate. A probable reaction mechanism is suggested. MAIK Nauka/ Interperiodica 2006.
- Grekov,Novakov
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- Phosphine synthesis via cathodic reduction of molten white phosphorus
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Cathodic reduction of molten phosphorus in an acid electrolyte with the formation of phosphine is studied. The results demonstrate that the process can be accelerated by sonication, which increases the current density corresponding to phosphine synthesis by a factor of 5, up to 1 A/cm2. It is shown that the electrochemical synthesis of phosphine is due to charge transport across the phosphorus film on the cathode. The optimized electrochemical synthesis conditions are described.
- Vorotyntsev,Mochalov,Balabanov
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- Electrolytic formation of phosphine from red phosphorus in aqueous solutions
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Data are presented on the current-voltage behavior of red phosphorus suspensions at gold, platinum, lead, and cadmium cathodes in a 1.0 M Na 2CO3 solution. In experiments with a red phosphorus suspension in alkaline solutions, the fo
- Shalashova,Smirnov,Nikolashin,Turygin,Khudenko,Brekhovskikh,Fedorov,Tomilov
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- REACTION OF SODIUM WITH IONIC CONDUCTORS CONTAINING P-O BONDS AT ELEVATED TEMPERATURES.
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Sodium phosphate and a series of compounds containing Na, Zr, Si, P, and O were found to react with sodium at 380 degree C. The reaction products formed phosphine on hydrolysis. On the basis of these reactions and some thermodynamic calculations, it is not likely that any materials containing P-O bonds will be stable to sodium at the temperatures required for the Na-S battery or Na heat engine operation.
- Tennenhouse,Crosbie
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- 2,4,6-Tri(hydroxy)-1,3,5-triphosphinine, P3C3(OH)3: The Phosphorus Analogue of Cyanuric Acid
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Cyanuric acid (C3H3N3O3) is widely used as cross-linker in basic polymers (often in combination with other crosslinking agents like melamine) but also finds application in more sophisticated materials such as in supramolecular assemblies and molecular sheets. The unknown phosphorus analogue of cyanuric acid, P3C3(OH)3, may become an equally useful building block for phosphorus-based polymers or materials which have unique properties. Herein we describe a straightforward synthesis of 2,4,6-tri(hydroxy)-1,3,5-triphosphinine and its derivatives P3C3(OR)3which have been applied as strong π-acceptor η6-ligands in piano stool Mo(CO)3complexes.
- Suter, Riccardo,Mei, Yanbo,Baker, Matthew,Benk?, Zoltan,Li, Zhongshu,Grützmacher, Hansj?rg
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- Organoactinide Phosphine/Phosphite Coordination Chemistry. Facile Hydride-Induced Dealkoxylation and the Formation of Actinide Phosphinidene Complexes
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This contribution reports a study of the reaction of the organoactinide hydrides (Cp'2MH2)2 (Cp'=η5-(CH3)5C5, M=Th,U) with trimethyl phosphite.Quantitative transposition of hydryde and methoxide ligands occurs to yield the corresponding Cp'2M(OCH3)2 complexes (synthesized independently from Cp'2MCl2 and NaOCH3) and the phosphinidene-bridged methoxy complexes 2PH.The reaction is considerably more rapid for M=U than for M=Th.The new compounds were characterized by elemental analysis, 1H and 31P NMR, infrared spectroscopy, magnetic susceptibility, and D2O hydrolysis.The molecular structure of 2PH has been determined by single-crystal X-ray diffraction techniques.It crystallizes in the monoclinic space group P2/n with a=13.926(3) Angstroem, b=10.765(3) Angstroem, c=15.282(4) Angstroem, β=107.63(2) deg, and Z=2.Full-matrix least-squares refinement of the structural parameters for the 24 independent anisotropic non-hydrogen atoms has converged to R1 (unweighted, based on F) = 0.041 for 1677 independent absorption-corrected reflections having 2ΘMoKα3?(I).The 2PH molecule has C2 symmetry, with the μ-PH2- ligand lying on a crystallographic twofold axis.The coordination geometry about each uranium ion is of the typical pseudotetrahedral Cp'2M(X)Y type, with U-P=2.743(1) Angstroem, U-O=2.046(14) Angstroem, U-P-U=157.7(2) deg, and U-O-C(methyl)=178(1) deg.Evidence is presented that other >P-OR linkages react in a similar manner.
- Duttera, Michael R.,Day, Victor W.,Marks, Tobin J.
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- Expedient Route to Chalcogenophosphinates with Glucose Moieties via Todd-Atherton-Like Coupling between Secondary Phosphine Chalcogenides and Diacetone- d -Glucose in the CCl4/Et3N System
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Secondary phosphine chalcogenides react with diacetone-d-glucose (DAG) in the system CCl4/Et3N (70°C, 4-24 h) to afford DAG chalcogenophosphinates in up to 79% yield, thus paving a short way to optically active chalcogenophosphinates with glucose moieties. As an example, a mild regioselective hydrolysis (70 °C, aqueous MeCOOH) of DAG bis(2-phenylethyl)selenophosphinate) obtained leads to monoacetone-d-glucose bis(2-phenylethyl)selenophosphinate.
- Volkov, Pavel A.,Ivanova, Nina I.,Gusarova, Nina K.,Sukhov, Boris G.,Khrapova, Kseniya O.,Zelenkov, Lev E.,Smirnov, Vladimir I.,Borodina, Tatyana N.,Vakul'Skaya, Tamara I.,Khutsishvili, Spartak S.,Trofimov, Boris A.
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- Intrinsic Barriers to Proton Exchange between Transition-Metal Centers: Application of a Weak-Interaction Model
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A weak-interaction model for proton self-exchange between transition-metal centers is considered.The rate constant obtained from the Fermi golden-rule expression of radiationless transition theory is a product of terms for assembling acid and base reactants at the correct orientation and distance, a classical reaction frequency, an electron-proton reaction probability, and classical nuclear factors deriving from the requirement for reorganization of ancillary ligands and solvent modes.It is found that such a model yields calculated rate constants and activation parameters in reasonable agreement with the experimental data, provided that the fluxionality of certain metal centers is taken into account.
- Creutz, Carol,Sutin, Norman
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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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- Synthesis of monophosphines directly from white phosphorus
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Monophosphorus compounds are of enormous industrial importance due to the crucial roles they play in applications such as pharmaceuticals, photoinitiators and ligands for catalysis, among many others. White phosphorus (P4) is the key starting material for the preparation of all such chemicals. However, current production depends on indirect and inefficient, multi-step procedures. Here, we report a simple, effective ‘one-pot’ synthesis of a wide range of organic and inorganic monophosphorus species directly from P4. Reduction of P4 using tri-n-butyltin hydride and subsequent treatment with various electrophiles affords compounds that are of key importance for the chemical industry, and it requires only mild conditions and inexpensive, easily handled reagents. Crucially, we also demonstrate facile and efficient recycling and ultimately catalytic use of the tributyltin reagent, thereby avoiding the formation of substantial Sn-containing waste. Accessible, industrially relevant products include the fumigant PH3, the reducing agent hypophosphorous acid and the flame-retardant precursor tetrakis(hydroxymethyl)phosphonium chloride. [Figure not available: see fulltext.]
- Scott, Daniel J.,Cammarata, Jose,Schimpf, Maximilian,Wolf, Robert
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p. 458 - 464
(2021/04/09)
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- Generation of a π-Bonded Isomer of [P4]4? by Aluminyl Reduction of White Phosphorus and its Ammonolysis to PH3
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By employing the highly reducing aluminyl complex [K{(NON)Al}]2 (NON=4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene), we demonstrate the controlled formation of P42? and P44? complexes from white phosphorus, and chemically reversible inter-conversion between them. The tetra-anion features a unique planar π-bonded structure, with the incorporation of the K+ cations implicit in the use of the anionic nucleophile offering additional stabilization of the unsaturated isomer of the P44?fragment. This complex is extremely reactive, acting as a source of P3?: exposure to ammonia leads to the release of phosphine (PH3) under mild conditions (room temperature and pressure), which contrast with those necessitated for the direct combination of P4 and NH3 (>5 kbar and >250 °C).
- Aldridge, Simon,Ellwanger, Mathias A.,Heilmann, Andreas,Roy, Matthew M. D.
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supporting information
p. 26550 - 26554
(2021/11/16)
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- Dual Role of Doubly Reduced Arylboranes as Dihydrogen- and Hydride-Transfer Catalysts
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Doubly reduced 9,10-dihydro-9,10-diboraanthracenes (DBAs) are introduced as catalysts for hydrogenation as well as hydride-transfer reactions. The required alkali metal salts M2[DBA] are readily accessible from the respective neutral DBAs and Li metal, Na metal, or KC8. In the first step, the ambiphilic M2[DBA] activate H2 in a concerted, metal-like fashion. The rates of H2 activation strongly depend on the B-bonded substituents and the counter cations. Smaller substituents (e.g., H, Me) are superior to bulkier groups (e.g., Et, pTol), and a Mes substituent is even prohibitively large. Li+ ions, which form persistent contact ion pairs with [DBA]2-, slow the H2-addition rate to a higher extent than more weakly coordinating Na+/K+ ions. For the hydrogenation of unsaturated compounds, we identified Li2[4] (Me substituents at boron) as the best performing catalyst; its substrate scope encompasses Ph(H)CNtBu, Ph2CCH2, and anthracene. The conversion of E-Cl to E-H bonds (E = C, Si, Ge, P) was best achieved by using Na2[4]. The latter protocol provides facile access also to Me2Si(H)Cl, a most important silicone building block. Whereas the H2-transfer reaction regenerates the dianion [4]2- and is thus immediately catalytic, the H--transfer process releases the neutral 4, which has to be recharged by Na metal before it can enter the cycle again. To avoid Wurtz-type coupling of the substrate, the reduction of 4 must be performed in the absence of the element halide, which demands an alternating process management (similar to the industrial anthraquinone process).
- Von Grotthuss, Esther,Prey, Sven E.,Bolte, Michael,Lerner, Hans-Wolfram,Wagner, Matthias
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supporting information
(2019/04/17)
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- Dual Role of Doubly Reduced Arylboranes as Dihydrogen- and Hydride-Transfer Catalysts
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Doubly reduced 9,10-dihydro-9,10-diboraanthracenes (DBAs) are introduced as catalysts for hydrogenation as well as hydride-transfer reactions. The required alkali metal salts M2[DBA] are readily accessible from the respective neutral DBAs and Li metal, Na metal, or KC8. In the first step, the ambiphilic M2[DBA] activate H2 in a concerted, metal-like fashion. The rates of H2 activation strongly depend on the B-bonded substituents and the counter cations. Smaller substituents (e.g., H, Me) are superior to bulkier groups (e.g., Et, pTol), and a Mes substituent is even prohibitively large. Li+ ions, which form persistent contact ion pairs with [DBA]2-, slow the H2-addition rate to a higher extent than more weakly coordinating Na+/K+ ions. For the hydrogenation of unsaturated compounds, we identified Li2[4] (Me substituents at boron) as the best performing catalyst; its substrate scope encompasses Ph(H)C=NtBu, Ph2C=CH2, and anthracene. The conversion of E-Cl to E-H bonds (E = C, Si, Ge, P) was best achieved by using Na2[4]. The latter protocol provides facile access also to Me2Si(H)Cl, a most important silicone building block. Whereas the H2-transfer reaction regenerates the dianion [4]2- and is thus immediately catalytic, the H--transfer process releases the neutral 4, which has to be recharged by Na metal before it can enter the cycle again. To avoid Wurtz-type coupling of the substrate, the reduction of 4 must be performed in the absence of the element halide, which demands an alternating process management (similar to the industrial anthraquinone process).
- Von Grotthuss, Esther,Prey, Sven E.,Bolte, Michael,Lerner, Hans-Wolfram,Wagner, Matthias
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supporting information
p. 6082 - 6091
(2019/04/17)
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- Exploring the Reactivity of Donor-Stabilized Phosphenium Cations: Lewis Acid-Catalyzed Reduction of Chlorophosphanes by Silanes
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Phosphane-stabilized phosphenium cations react with silanes to effect either reduction to primary or secondary phosphanes, or formation of P-P bonded species depending upon counteranion. This operates for in situ generated phosphenium cations, allowing catalytic reduction of P(III)-Cl bonds in the absence of strong reducing agents. Anion and substituent dependence studies have allowed insight into the competing mechanisms involved.
- Pearce, Kyle G.,Borys, Andryj M.,Clark, Ewan R.,Shepherd, Helena J.
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supporting information
p. 11530 - 11536
(2018/09/21)
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- Inorganic Triphenylphosphine
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A completely inorganic version of one of the most famous organophosphorus compounds, triphenylphosphine, has been prepared. A comparison of the crystal structures of inorganic triphenylphosphine, PBaz3 (where Baz=B3H2N3H3) and PPh3 shows that they have superficial similarities and furthermore, the Lewis basicities of the two compounds are remarkably similar. However, their oxygenation and hydrolysis reactions are starkly different. PBaz3 reacts quantitatively with water to give PH3 and with the oxidizing agent ONMe3 to give the triply-O-inserted product P(OBaz)3, an inorganic version of triphenyl phosphite; a corresponding transformation with PPh3 is inconceivable. Thermodynamically, what drives these striking differences in the chemistry of PBaz3 and PPh3 is the great strength of the B?O bond.
- Gorman, Adam D.,Bailey, Jonathan A.,Fey, Natalie,Young, Tom A.,Sparkes, Hazel A.,Pringle, Paul G.
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supporting information
p. 15802 - 15806
(2018/11/23)
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- A new access to tri(1-naphthyl)phosphine and its catalytically active palladacycles and luminescent Cu(I) complex
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New approach to synthesis of tri(1-naphthyl)phosphine (Np3P) and its application for design of new Pd(II) and Cu(I) complexes are reported. This phosphine has been prepared in 32% yield through exhaustive P–H arylation of РН3 with 1-chloronaphthalene in the superbasic t-BuOK/DMSO system at 70 °C. The Np3P was found to readily reacts with chloro-bridged dimers, [(κ2-C,N)Pd(μ-Cl)]2 (κ2-C,N = PhCH2NMe2 (2a) or FcCH2NMe2 (2b), to give new mononuclear palladacycles [(κ2-C,N)Pd(Np3P)Cl] (3, 4), in which metal has a square-planar geometry. These complexes show good catalytic activity in the Sonogashira reaction under low catalyst loadings (2 mol% Pd) and relatively mild conditions. We also synthesized and characterized first Cu(I) complex with Np3P, namely, [Cu(phen)(Np3P)I], that exhibits red emission (λmax = 650 nm) at room temperature.
- Artem'ev, Alexander V.,Kuimov, Vladimir A.,Matveeva, Elena A.,Bagryanskaya, Irina Yu.,Govdi, Anastasia I.,Vasilevsky, Sergey F.,Rakhmanova, Mariana I.,Samultsev, Dmitry O.,Gusarova, Nina K.,Trofimov, Boris A.
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- Reaction of 1-bromonaphthalene with PH3 in the t-BuOK/DMSO system: PCl3-free synthesis of di(1-naphthyl)phosphine and its oxide
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The phosphine, generated together with hydrogen from red phosphorus and aqueous KOH, reacts with 1-bromonaphthalene in the t-BuOK/DMSO system under mild conditions (70 °C, atmospheric pressure) to give di(1-naphthyl)phosphine, which is easily oxidized in the presence of air to afford di(1-naphthyl)phosphine oxide in 45% preparative yield. Tri(1-naphthyl)phosphine and naphthalene are also formed in the reaction in 23 and 27% yield, respectively. According to ESR and UV data, the studied phosphination of 1-bromonaphthalene involves a single electron transfer process.
- Kuimov, Vladimir A.,Matveeva, Elena A.,Khutsishvili, Spartak S.,Vakul'skaya, Tamara I.,Sinegovskaya, Lidiya M.,Malysheva, Svetlana F.,Gusarova, Nina K.,Trofimov, Boris A.
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supporting information
p. 4723 - 4729
(2017/07/17)
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- Synthesis of tris[2-(2-furyl)ethyl]phosphine its chalcogenides and PdII complex
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Nucleophilic addition of PH3 to 2-vinylfuran in the KOH/DMSO(H2O) suspension affords 65% of tris[2-(2-furyl)ethyl]-phosphine, whose treatment with H2O2, Se or PdCl gives the corresponding phosphine oxide, selenide and complex of trans-[Pd(L)2Cl2] type in good to excellent yields.
- Artem'ev, Alexander V.,Gusarova, Nina K.,Sutyrina, Anastasiya O.,Gatilov, Yurii V.,Trofimov, Boris A.
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p. 314 - 316
(2016/08/09)
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- Direct phosphorylation of fullerene C60 with phosphine
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Fullerene C60 reacts with phosphine (PH3) under free radical initiation conditions (azobis(isobutyronitrile), xylene, 65°C, 6–11 h) to give in the presence of air oxygen functional oligofullerenes (yield up to 32%) containing functional groups of phosphinic and phosphonic acids.
- Kuimov,Matveeva,Malysheva,Samul’tsev,Gusarova,Khutsishvili,Vakul’skaya,Trofimov
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p. 321 - 324
(2016/12/14)
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- Synthesis and properties of a new family of phosphorus- and nitrogen-containing ionenes
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Polyquaternization reactions of bis[2-(4-pyridyl)ethyl]phenylethylphosphine oxide and tris[2-(4-pyridyl)ethyl]phosphine oxide with 1,4-dibromobutane were implemented for the first time to give linear (water-soluble) and cross-linked (limitedly water swelling), respectively, representatives of new phosphorus- and nitrogen-containing ionenes. The synthesized linear ionenes react with heparin and polyacrylic acid yielding water-insoluble polyelectrolyte complexes.
- Mikhailenko,Kizhnyaev,Verkhoturova,Apartsin,Gusarova,Grigor'Ev,Trofimov
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p. 286 - 290
(2016/01/09)
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- Effect of a sacrificial anode material on the electrochemical generation of phosphane oxide (H3PO)
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The highest yields of phosphane oxide in the title process were obtained in electrochemical cells supplied with aluminium (49%), tin (36%) or zinc (67%) anodes.
- Gorbachuk, Elena V.,Khayarov, Khasan R.,Sinyashin, Oleg G.,Yakhvarov, Dmitry G.
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p. 334 - 335
(2015/02/19)
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- Electrochemical generation of P4 2- dianion from white phosphorus
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Electrochemical reduction of elemental (white) phosphorus in an undivided cell equipped with a sacrificial metal anode (Al, Co, Nb, Sn) results in the formation of the reduced form of white phosphorus, P4 2- dianion, which was detected in solution by 31P NMR spectroscopy.
- Yakhvarov,Gorbachuk,Khayarov, Kh. R.,Morozov,Rizvanov, I. Kh.,Sinyashin
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p. 2423 - 2427
(2015/08/03)
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- Nucleophilic addition of phosphine to 4-chlorostyrenes in the KOH-DMSO system
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In the superbasic system KOH-DMSO (H2O) at 60-75 °C (2-2.5 h, atmospheric pressure), 4-chlorostyrene and 4-chloro-α-methylstyrene add phosphine at the double bond to form 1: 1 and 2: 1 anti-Markovnikov adducts in 10-18% and 58-67% yields, respe
- Artem'Ev,Malysheva,Gusarova,Korocheva,Timokhina,Trofimov
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p. 2495 - 2497
(2014/11/08)
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- Frustrated lewis pair route to hydrodesilylation of silylphosphines
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A 1:1 mixture of P(SiMe3)3 and B(p-C 6F4H)3 reacts with 3 equiv of 4-heptanone to afford a 1:2 mixture of [(Me3SiO)(n-Pr)2C]H 2P-B(p-C6F4H)3 and the silyl enol ether, 4-trimethylsiloxy-3-heptene. Subsequent thermolysis of the adduct produces H3P-B(p-C6F4H)3 and an additional equiv of silyl enol ether. In the presence of a catalytic quantity of B(p-C6F4H)3, however, P(SiMe3) 3 reacts with 4-heptanone to produce a 1:1 mixture of [(Me 3SiO)(n-Pr)2C]2PH and silyl enol ether. Heating this mixture further produces [(Me3SiO)(n-Pr)2C]PH 2, which is eventually converted to elemental phosphorus.
- Takeuchi, Katsuhiko,Hounjet, Lindsay J.,Stephan, Douglas W.
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supporting information
p. 4469 - 4472
(2013/09/23)
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- Experimental evidence of phosphine oxide generation in solution and trapping by ruthenium complexes
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Phosphine oxide (H3PO), the first defined compound of phosphorus in the oxidation state -1, was obtained in solution by electrochemical methods starting from white phosphorus (see picture). H3PO was characterized by NMR solution spectroscopy as a free molecule and isolated as a ligand in ruthenium(II) complexes following tautomerization to phosphinous acid, H 2P(OH).
- Yakhvarov, Dmitry,Caporali, Maria,Gonsalvi, Luca,Latypov, Shamil,Mirabello, Vincenzo,Rizvanov, Ildar,Sinyashin, Oleg,Stoppioni, Piero,Peruzzini, Maurizio
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p. 5370 - 5373
(2011/07/07)
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- Synthesis of volatile inorganic hydrides by electrochemical method
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Published data and results of our investigations on the problem of electrochemical synthesis of arsenic, phosphorus, and germanium hydrides are generalized. The results of the developments of the physicochemical bases of arsine synthesis by electrochemical reduction of arsenic acid, phosphine by reduction of white phosphorus in organic solvents, and monogermane by reduction of germanate in basic conditions are reported. The current yield of hydrides is 95, 90, and 40%, respectively. The promising guidelines of the practical use of electrochemical methods of the synthesis of the hydrides in the manufacture of semiconductor materials for microelectronics, optics, and laser engineering are discussed. The development of an arsine generator attracts considerable interest, which can serve as a basis for an aggregative continuous apparatus used in complex flow charts of manufacture of semiconductor materials.
- Turygin,Tomilov,Berezkin, M. Yu.,Fedorov
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p. 1459 - 1478
(2011/02/28)
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- Electrochemical synthesis of phosphine from the lower phosphorus acids
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We have studied the reduction of hypophosphorous and phosphorous acids at mercury and lead cathodes and with potassium and sodium amalgams. Both acids are found to be difficult to reduce. With the mercury cathode, the current efficiency for phosphine is w
- Turygin,Smirnov,Khudenko,Nikolashin,Fedorov,Tomilov
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p. 1388 - 1393
(2010/04/04)
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- High gas storage capacities for ionic liquids through chemical complexation
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Gases with sufficient Lewis acidity or basicity form weak and reversible complexes with carefully selected ionic liquids. We have prepared ionic liquid complexes with PH3 and BF3 that provide large gas capacities in the liquid phase
- Tempel, Daniel J.,Henderson, Philip B.,Brzozowski, Jeffrey R.,Pearlstein, Ronald M.,Cheng, Hansong
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p. 400 - 401
(2008/09/19)
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- Preparation of high-performance nanosized palladium hydrogenation catalysts using white phosphorus and phosphine
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The nature and properties of nanosized palladium hydrogenation catalysts modified with elemental phosphorus and phosphine (PH3) were studied.
- Belykh,Skripov,Belonogova,Umanets,Shmidt
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p. 1523 - 1528
(2008/03/27)
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- Molecular lead clusters - From unexpected discovery to rational synthesis
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Feats of lead: The cluster compounds [Pb12Hyp6] (1; see structure) and [Pb10Hyp6] (2) result from the reaction of the plumbylene [Pb{Si(SiMe3)3}2] ([PbHyp2]) with hydride sources, such as PH3 or [{(Ph 3P)CuH}6]. They are the first examples of neutral lead clusters bearing σ-bonded substituents. Whereas 2 is isolated from the reaction mixture on a multigram scale, 1 is only obtained in traces.
- Klinkhammer, Karl W.,Xiong, Yun,Yao, Shenglai
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p. 6202 - 6204
(2007/10/03)
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- Reactivity of electron-poor decamethyl-1,3-diboraruthenocene with sulfur and phosphorus compoundsDedicated to Professor Bernt Krebs on the occasion of his 65th birthday
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Decamethyl-1,3-diboraruthenocene [(η5-C5 Me5)Ru{η5-(CMe)3(BMe)2}] (1) reacts with cyclo-octasulfur in hexane to give [(η5 -C5Me5){η5-(CMe)3 (BMe)2}Ru=S] (3), which may also be obtained from 1 and propylene sulfide. 1 reacts with H2S to form the ruthenathiacarboranyl complex [(η5-C5 Me5)Ru{η4-(CMe)3(BMe)2S}] (6), for which a nido-structure is proposed. The isomeric compounds 3 and 6 have different stabilities: 3 loses sulfur and unexpectedly the closo-cluster [(η5-C5Me5) 2Ru2H(CMe)3(BMe)2] (4) is formed with hydrogen bridging the basal and apical Ru centers. Reaction of 1 with carbonylsulfide (COS) yields the dinuclear ruthenium compound [(η5-C5Me5)Ru{η5 -(CMe)3(BMe)2(S)(COBMe)}]2 (7) in which two B-O groups bridge two ruthenium complexes. Its formation results from a complex reaction sequence: sulfur inserts into the diborolyl ring and the ligand CO forms an oxygen-boron bridge to a second molecule, followed by insertion of the carbonyl carbon into the double bond of the diboraheterocycle. Carbon disulfide reacts with 1 to give the dinuclear complex 8 with two CS2 molecules connecting the ruthenium centers. When 1 and P4 are heated in toluene, the sandwich 9 is obtained by formal i nsertion of a P-H group into the diborolyl ring of 1 and the triple-decker [{η5-(C5Me5)Ru }2{μ-(MeC)3P(MeB)2} (10) is detected in the mass spectrum. The phosphaalkyne P≡CtBu inserts into 1 to give the ruthenaphosphacarborane [(η5 -C5Me5)Ru{(CMe)2(BMe)(PC t Bu)(CMe) (BMe)}] (11) in high yield. Phosphanes react with 1 to give weak donor-acceptor complexes 1 · PH2R (12) (R=Ph, H). The compositions of the compounds are deduced from spectroscopic and analytical data and are confirmed for 4 and 7 by X-ray structural analyses.
- Bach, Bettina,Nie, Yong,Pritzkow, Hans,Siebert, Walter
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p. 429 - 437
(2007/10/03)
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- Thermal disproportionation of hypophosphorous acid
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Thermal disproportionation of hypophosphorous acid was studied to find the reaction order, the rate constant and activation energy of the process, and also the temperature ranges in which the reaction rate is the highest.
- Shechkov,Pevneva,Meshkova
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p. 1354 - 1355
(2007/10/03)
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- Synthesis and molecular structure of fluoro(triphosphanyl)silane and attempts to synthesize a silylidyne-phosphane
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The synthesis, isolation, spectroscopic characterization (IR, multi-nuclear NMR) and single-crystal X-ray diffraction analysis of FSi(PH2)3 (1a), the first isolable fluorophosphanylsilane, is reported along with the gas phase decomposition of 1a, MeSi(PH2)3 (1b) and EtSi(PH2)3 (1c) under flash vacuum or pulsed pyrolysis conditions and matrix isolation of the products. The title compound is formed quantitatively by PH2/F-ligand exchange reaction of tetraphosphanylsilane Si(PH2)4 with the difluorodiarylstannane Is2SnF2 (Is=2,4, 6-triisopropylphenyl) in the molar ratio of 1:1 in benzene as solvent. Since 1a cannot be separated from the solvent by fractional condensation its isolation was achieved by means of preparative GC. A single crystal of 1a (triclinic, Pl?) suitable for X-ray diffraction analysis was grown by in situ crystallization on a diffractometer at 175 K through miniaturized zone melting with focused infra-red radiation. Interestingly, the Si atom is remarkably distorted tetrahedral coordinated with F-Si-P angles of 120.4(7), 110.4(7), 106.3(1)° and normal Si-F (1.60(2) ?) and Si-P distances (av. 2.241(2) ?). According to ab initio (MP2/6-31G(d,p); MP2/6-311G(2d,p)) and DFT calculations (BLYP, B3LYP, B3PW91 functionals), the distortion is not an intrinsic property of the molecule but due to crystal packing forces. The best agreement between the experimental versus calculated geometrical and vibrational data is achieved at the B3PW91/6-311G(2d,p) level of theory. Since 1a-c appeared as potential precursors for the respective silylidyne-phosphanes ('silaphospha-acetylene') RSiP through stepwise extrusion of PH3, some thermodynamical data for the decomposition and the relative energies of linear RSiP versus bent :SiPR isomers (R=H, Me, Et, Pr, Ph, CF3, OMe, halogen and SiH3) were also calculated. The latter revealed that electronegative substituents R favor the Si-P triple bond in RSiP (except for R=CF3 which stabilizes the :SiPR form) while strong σ-donating substituents R (H, SiH3) favor the :SiPR isomer with Si-P double bond. Although elimination of PH3 and other fragmentation products could be detected by controlled thermal decomposition and matrix isolation, neither flash vacuum experiments of 1a, 1b and 1c (400-600 °C) nor pulsed pyrolyses of 1a at (1100 °C) did provide any direct evidence for the formation of the desired species with Si-P multiple bonds.
- Driess, Matthias,Monsé, Christian,Bl?ser, Dieter,Boese, Roland,Bornemann, Holger,Kuhn, Arvid,Sander, Wolfram
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p. 294 - 305
(2007/10/03)
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- The ground vibrational states of PH2D and PHD2
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The high resolution (2.3-3.1 × 10-3 cm-1) Far infrared Fourier transform spectrum of PH2D and PHD2 was recorded in the 20-160 cm-1 region. Assignments were made using a specially developed computer-assisted automatic 'two pair transition' method. Altogether, 1300 and 590 infrared transitions of the PHD2 and PH2D species, respectively, were fitted together with appropriately weighted microwave transitions to derive the rotational and centrifugal distortion parameters up to eighth order of the ground vibrational states of both molecules. The parameters obtained from these fits reproduce the microwave transitions with accuracies close to experimental uncertainties. A few of microwave transitions were shown to be blended, or misassigned. The rms deviations for the infrared data are 1.01 × 10-4 and 1.05 × 10-4 cm-1 for PH2D and PHD2, respectively, which is also close to the experimental uncertainty.
- Ulenikov,Bürger,Jerzembeck,Onopenko,Bekhtereva,Petrunina
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p. 225 - 237
(2007/10/03)
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- Contributions to the chemistry of phosphorus. 241. On the reaction of diphosphane(4) with liquid ammonia and with amines - A new route to polyphosphides and hydrogen polyphosphides
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Diphosphane(4), P2H4, reacts with liquid ammonia in the temperature range -76 °C to -40 °C to furnish a mixture of the ammonium polyphosphides (NH4)2H2P14, (NH4)2P16, (NH4)3P19, and (NH4)3P21, in addition to PH3. The first intermediate product detectable by NMR spectroscopy is the bicyclic compound NH4H4P7, which reacts further with P2H4 to afford the more phosphorus-rich polycyclic phosphides. On removal of the ammonia the hydrogen polyphosphide (NH4)2H2P14 decomposes with formation of PH3 and hydrogen-free, more phosphorus-rich polyphosphides. When the reaction of diphosphane(4) with liquid ammonia is performed in the presence of tetrahydrofuran the final products are the hydrogen polyphosphides NH4H4P7 and NH4H5P8 together with PH3; the hydrogen-rich, open-chain heptaphosphide NH4H8P7 has been identified as a precursor. An investigation of the behavior of diphosphane(4) towards amines using the primary amine ethylenediamine as an example at +10 °C in the absence of a solvent or in the presence of tetrahydrofuran resulted in the formation of a polyphosphide mixture consisting of (C2H4N2H5)2P 16, (C2H4N2H5)3P 21, and (C2H4N2H5)3P19 as well as some PH3. No reaction occurred with the secondary and tertiary amines diethylamine and tetramethylethylenediamine (TMEDA), respectively, even at room temperature.
- Baudler,Winzek
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p. 417 - 422
(2008/10/08)
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- Protonation and hydrogen atom abstraction reactions in the synthesis of the [HP7M(CO)3]2- ions (M = Cr, W)
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Ethylenediamine (en) solutions of [P7M(CO)3]3- (M = Cr, W) react with weak acids to give [HP7M(CO)3]2- ions where M = Cr (4 a) and W (4b) in high yields. Competition studies with known acids revealed a pKa range for 4 b in DMSO of 17.9 to 22.6. The [P7M(CO)3]3- complexes also react with one-half equivalent of I2 to give 4 through an oxidation/hydrogen atom abstraction process. Labeling studies show that the abstracted hydrogen originates from the [K(2,2,2-crypt)]+ ions or from the solvent (DMSO-d6) in the absence of [K(2,2,2-crypt)]+ or other good hydrogen atom donors. In the solid state, the ions have no crystallographic symmetry but in solution they show virtual Cs symmetry (31P NMR spectroscopy) due to an intramolecular wagging process. Crystallographic data for [K(2,2,2-crypt)]2[HP7W(CO)3]: triclinic, P1, a = 10.9709(8) A, b = 13.9116(10) A, c = 19.6400(14) A, α = 92.435(6)°, β = 93.856(6)°, γ = 108.413(6)°, V = 2831.2(4) A3, Z = 2, R(F) = 7.65%, R(wF2) = 14.17% for all 7400 reflections. For [K(2,2,2-crypt)]2[HP7Cr(CO)3]: triclinic, P1, a = 12.000(3) A, b = 14.795(3) A, c = 17.421(4) A, α = 93.01(2)°, β = 93.79(2)°, γ = 110.72(2)°, V = 2877(2) A3, Z = 2. Johann Ambrosius Barth 1998.
- Charles, Scott,Danis, Janet A.,Mattamana, Sundeep P.,Fettinger, James C.,Eichhorn, Bryan W.
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p. 823 - 829
(2008/10/09)
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- Comparative Ab initio and Hybrid DFT Studies Relevant to an Experimental Investigation of Neutral and Cationic [Si, P, H2] Isomers
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The neutral and the lowest cationic (singlet and triplet) potential-energy surfaces of (Si, P, H2] have been explored by means of ab initio MO calculations at the G2 level of theory as well as the hybrid DFT (B3LYP/6-311G**) method. Contrary to the neutral and triplet surfaces, where the H2SiP+ 0isomers represent the global minima, for the singlet cation a doubly bridged P(H)2Si+ structure has been identified as the most stable isomer, with the non-bridged H2SiP+ species being significantly less stable (ΔE = 31.7 kcal mol-1 at G2). As far as the comparison of the two quantum-chemical methods (i.e. G2 and B3LYP) is concerned, the calculated relative energies ΔE are quite close to each other, with deviations smaller than 4 kcal mol-1. However, while the non-bridged SiPH2+ (1A') represents a minimum at the G2 level, it could not be located using the hybrid DFT method. The computationally predicted singlet and triplet |Si, P, H2]+ potential-energy surfaces provide insight into the course of the ion/molecule reactions of Si+ with phosphine and P+ with silane, respectively, which were examined experimentally. Thus, the reaction of the doublet species Si+ with phosphine allows access to the nonclassical, bridged P(H)2Si+ structure, while in the reaction of the P+ triplet cation with silane, no evidence for Si-P bond formation is obtained.
- Hrusak, Jan,Schroeder, Detlef,Schwarz, Helmut,Iwata, Suehiro
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p. 777 - 787
(2007/10/03)
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- Ba11KX7O2 (X = P, AS): Two novel zintl phases with infinite chains of oxygen centered Ba6 octahedra, isolated X3- and dimeric X24- anions
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Reactions of BaX (X = P, As) with Ba, K and BaO in tantalum tubes at 900-1000°C yielded black, very air-and moisture-sensitive crystals of Ba11KP7O2 and isotypic Ba11KAs7O2 which were characterized by EDX and X-ray diffraction (orthorhombic, Fddd, Z = 8; a = 1069.9(1), b = 1514.3(2), c = 3164.6(4) pm and a = 1087.8(2), b = 1542.3(2), c = 3232.4(4) pm, respectively). The structure contains infinite zigzag chains, 1∞[Ba4Ba2/2O], of oxygen-centered, corner-sharing Ba6 octahedra along [100]. They are connected by linear strings built of alternating isolated X atoms and X2 dimers to form layers parallel to (001). While the isolated X atoms are surrounded by eight Ba forming a distorted cube, the X2 dimers center a Ba12 polyhedron which is comprised of a pair of face-sharing Ba square antiprisms. This results in a cube-antiprism-antiprism-cube sequence of face-sharing Ba polyhedra. Additional X atoms function as spacers between the layers and connect them along [001]. Two atom positions are statistically occupied by Ba and K, and the formula may be written as Ba2+11K+X3-5(X 2)4-O2-2 according to the Zintl-Klemm concept.
- Lulei, Michael
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p. 1796 - 1802
(2008/10/09)
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- Reduction of Oxygen Compounds of Vanadium(V), Chromium(VI), and Manganese(VII) by Phosphine and Arsine in the Presence of Halide Ions: Assessment of Activation Parameters
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Halide ions (X(-)=Cl(-), Br(-), I(-)) significantly accelerate the PH3 and AsH3 (EH3) oxidation in acid solutions to phosphorus and arsenic acids by oxygen compounds of vanadium(V), chromium(VI), and manganese(VII). The reaction rate increases with an increase of the concentrations of these reagents, catalysts, or hydrogen ions, as well as upon replacement of Cl(-) by Br(-) or I(-) ions, of PH3 by AsH3, and of vanadium(V) by Cr(VI) or Mn(VII). The kinetic methods with the use of free-radical inhibitors showed that the reaction proceeds through the formation of halophosphine or haloarsine metal complexes and the inner-sphere interaction of EH3 molecules with the halide ions, promoting two-electron redox decomposition of the intermediate, reduction of the metal ions, and formation ofhalophosphine or haloarsine (EH2X). The latter compounds are halogenate d in a similar way to phosphorus and arsenic halides (MX3), which hydrolyze to the corresponding acids. The total energy of the intermediate as a function of the EH3 deflection angle from the equilibrium position toward the halide ion, a potential barrier emerges, which is used as an index of reaction ability. The barrier value correlates with the activationand kinetic parameters of the reactions. This value decreases upon the substitution of Cl(-) by Br(-) or I(-) ions; PH3, by AsH3; and vanadium( V), by Cr(VI) or Mn(VII).
- Dorfman, Ya. A.,Polimbetova, G. S.,Doroshkevich, D. M.
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p. 636 - 644
(2008/10/08)
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- Contributions to the Chemistry of Phosphorus. 235. On the Preparation ofLarger Amounts of Diphosphane(4) in the Laboratory
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The preparation of several hundred grammes of diphosphane(4) by hydrolysis of calcium phosphide in a semicontinuous process as well as the handling of larger amounts of this compound are reported. In comparison with earlier results [12], the yield has been raised by 37 percent with simultaneous increase of the accessible total amount. The white solid which is formed in the preparation and purification of diphosphane(4) is not, as was believed in earlier work [25,8], triphosphane(5) or another, novelphosphorus hydride but is rather a clathrate compound of diphosphane(4) or the phosphanes PnHn+2 (n=2-4) and water, respectively.
- Baudler, M.,Staendeke, H.,Borgardt, M.,Strabel, H.,Dobbers, J.,et al.
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- Contributions to the Chemistry of Phosphorus. 236. On Several Physical and Chemical Properties of Diphosphane(4)
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The density of diphosphane(4) has been measured between -78°C and+18°C and the value d(20)4=1.014+/-0.002 extrapolated. the refra ctive index of P2H4 was determined to be n(20)=1.66+/-0.01. The surface tension at 0°C and -50°C was measured to be σ=34 and2 dyn*cm^-1, respectively. In the UV absorption spectrum, gaseous P2H4 exhibits a broad absorption band at λmax=2220 A, in n-hexane solu tion, this band is shifted somewhat to shorter wave-lengths. The molar extinction coefficient was determined to be ε~900 l*mol^-1*cm^-1. As a result of photolytic decomposition, absorptions for PH3 and more phosphorus-rich hydrides also occur. The solubility behavior of P2H4 in various organic solvents and the stabilities of the resultant solutions have been investigated. At 0°C, the solubility of diphosphane(4) in water was found to be 0.035+/-0.003 g P2H4/100 g solution and that of water in diphosphane(4) to be 43.2+/-1.6 g H2O / g solution. Thesystem diphosphane/methanol also exhibits a miscibility anomaly. The IR spectra of liquid P2H4 and of its solutions in various solvents reveale d, in accord with the results of nuclear magnetic resonance spectroscopy[7], that diphosphane(4) is practically not associated. Weak interactions through hydrogen bridging bonds occur with pyridine and methanol in which P2H4 serves as the proton donor and, in the latter case, also as proton acceptor. For the thermolysis of diphosphane(4), it has been found that the primary step comprises a disproportionation with intermolecular elimination of PH3 and formation of triphosphane(5). With further progress of thermolysis, in dependence on the reaction conditions, mixtures ofvarious phosphanes of differing composition are formed. Photolysis give s rise to phosphane mixtures having similar compositions. With aqueous silver salt and iodine solutions, diphosphane(4) reacts as a reducing agent; with sodium hydroxide solution, it reacts by a slow disproportionation as well as by formation and degradation of the subsequently formed pohyphosphides. On reacton with triphenylmethyl, triphenylmethane and a yellow solid of varying composition are formed. The reaction of diazomethane with diphosphane(4) leads to the preferential insertion of the carbene in the P-P bond and formation of methylenebis(phosphane).
- Baudler, M.,Dobbers, J.,Schoener, Ch. P.,Borgardt, M.,Rackwitz, D.,Krause, U. M.
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- Contributions to the Chemistry of Phosphorus. 237. On the Reaction of Diphosphane(4) with Peroxo Compounds: Formation of Phosphinophosphinic Acid, H2PPH(O)OH, and Bis(phosphino)phosphinic Acid, (H2P)2P(O)OH
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Diphosphane(4) reacts with peroxo compounds such as hydrogen peroxide, tetraline hydroperoxide, trifluoroperoxyacetic acid, and cumene hydroperoxide (which is particularly suited for preparative work) at -30°Cto furnish phosphinophosphinic acid, H2PP(O)OH (1), as the primary prod uct. Compound 1 disproportionates to a major extent in statu nascendi togive phosphanes (above all PH3) and monophosphorus acids of various oxi dation states as well as some bis(phosphino)phosphinic acid, (H2P)2P(O)OH (2). The acids 1 and 2 can be trapped and stabilized as their triethylammonium salts. The structures of these salts have been determined by spectroscopic investigations.
- Baudler, M.,Heumueller, H.
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- LOW-TEMPERATURE OXIDATION OF RED PHOSPHORUS
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The oxidation kinetics of red phosphorus in the low-temperature region have been investigated, and conditions favorable for the accumulation of various oxidation products (H3PO2, H3PO3, and H3PO4) have been determined.
- Shechkov, G. T.,Domin, A. V.,Neskorodova, N. M.
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p. 1501 - 1504
(2007/10/02)
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- The First Hydrides of a Phosphorus Sulfide Cage: Nuclear Magnetic Resonance Evidence for α-Tetraphosphorus Trisulfide Hydride Compounds
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The hydrides α-P4S4(H)R (R = H, I, NMePh or SPh) have been prepared in solution by the reaction of α-P4S3I2 or of the corresponding α-P4S3(I)R with Sn-n-Bu3H, and identified by 31P NMR spectroscopy.The compounds were unstable and not isolated.Ab initio molecular orbital calculations of geometry have been carried out for α-P4S3H2, α-P4S3(NMe2)2 and α-P4S3H(NMe2).
- Tattershall, Bruce W.,Kendall, Nigel L.
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p. 3163 - 3168
(2007/10/02)
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- Formation and NMR Spectroscopic Characterization of the Fluorophosphonium Cations, PH4-nFn+ (n = 1-4)
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The preparations of the salts PH3F+SbF6- and PHF3+Sb2F11- are reported.All fluorophosphonium cations PH4-nFn+ are characterized by multinuclear (1H, 19F, 31P) NMR spectroscopy.For n > 1 these salts are easily accessible by fluoride abstraction from fluorohydridophosphates(V).PH3F+SbF6-, however, is obtained in the reaction of PH3F2 with SbF5. - keywords: Fluorophosphonium Salts, Formation, NMR Spectra
- Minkwitz, Rolf,Liedtke, Andreas
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p. 679 - 682
(2007/10/02)
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- Reactions of Phosphine, Arsine, and Stibine with Carbonylbis(triethylphosphine)iridium(I) halides. Part 2. Reactions in Dichloromethane
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In CD2Cl2, as in toluene, AsH3 and SbH3 react with trans- , by oxidative addition.With PH3, the product of the initial reaction at 180 K gives +, (3).In the presence of excess of PH3, (3) is converted into tH3)(P'cH2)>+, (4) (c and t imply cis and trans respectively to hydride).All these species were identified by 1H and 31P n.m.r. spectroscopy.The spectra show that P't is much more basic than P'c; P'tH3 in (4) can be deprotonated by NMe3, to give tH2)(P'cH2)>, (5), and P'cH2 in (4) can be protonated with excess of HCl to give tH3)(P'cH3)>2+, (6).Compound (5) reacts with B2H6 to give tH2BH3)(P'cH2BH3)>, (9); compound (4) reacts with a half-molar proportion of B2H6 to give (6) and (9).Reaction of6-MeC6H4CHMe2-p)>2>, (10), with (5) in a 1:1 molar ratio gives 6-MeC6H4CHMe2-p)>2>, (11); with a 2:1 molar ratio, the initial product appears to be tH2RuCl2(η6-MeC6H4CHMe2-p)>(P'cH2)>, but on standing at room temperature for several hours this gives tH2)(μ-P'cH2)RuCl(η6-MeC6H4CHMe2-p)>. tH3)(μ-P'cH2)RuCl2(η6-MeC6H4CHMe2-p)> was formed from (4) and (10), and this could be deprotonated with NMe3.Reactions of (5) with (nbd=bicyclohepta-2,5-diene) and with (cod=cyclo-octa-1,5-diene) are also described.
- Ebsworth, E. A. V.,Mayo, Richard A.
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p. 477 - 484
(2007/10/02)
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- REACTION OF SALTS OF HYPOPHOSPHOROUS ACID WITH ALKYLHALIDES
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Alkali salts of hypophosphorous acid undergo an exchange reaction with alkyl halides.From the interaction between potassium hypophosphite and allyl bromide or 3-chloro-1,2-propanediol phosphonous acids are formed.A mechanism of the interaction, a variant of the Michaelis-Becker reaction, is proposed.
- Devedjiev, I.,Ganev, V.,Stefanova, R.,Borissov, G.
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p. 261 - 266
(2007/10/02)
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- Thermal decomposition of dihypophosphito - (UREA) - copper(II)
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The physico-chemical properties of the newly synthesized complex Cu(H2PO2)2CO(NH2)2 were investigated. The unit cell parameters and the mode of coordination of the urea molecule were determined. The thermal decomposition of the complex, which displays a topochemical character, was studied by thermogravimetric and mass-pectrometric methods. The end-products of the decomposition were detected. The activation energies of the process in the temperature ranges 323-330 K are 23.4 ± 1.4 and 20.64 ± 2.2 kcal/mol, respectively.
- Yagodin A.
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p. 537 - 542
(2008/10/08)
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- Contributions to the Chemistry of Phosphorus, 188. - Halogen-Substituted Cyclohexaphosphanes: Formation and Properties of (PCl)6 and (PBr)6
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Hexachlorocyclohexaphosphane (1) and hexabromocyclohexaphosphane (2) are formed in the partial dehalogenation of phosphorus trichloride and phosphorus tribromide, respectively, by magnesium or lithium hydride in polar solvents.As the first perhalogenated cyclophosphanes they are only stable in diluted solutions at low temperature and could be characterized by means of mass spectrometry and 31P nuclear magnetic resonance.Like the known hexaphenylcyclohexaphosphane, but in contrast to the parent compound P6H6, 1 and 2 have a six-membered phosphorus ring skeleton, which is obviously stabilized by electronegative substituents.
- Baudler, Marianne,Grenz, Detlef,Arndt, Uwe,Budzikiewicz, Herbert,Feher, Magda
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p. 1707 - 1710
(2007/10/02)
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- Preparation of new bis(dialkylamino)phosphine species via reduction of bis(dialkylamino)halophosphines
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Four new bis(dialkylamino)phosphine species, (Me2N)2PH, CH3NCH2CH2N(CH3)PH, (CO)3Ni[(Me2N)2PH], and (CO)3Ni-[CH3NCH2CH2N(CH 3)PH], have easily been prepared in good yields through reduction of corresponding bis(dialkylamino)-halophosphines by lithium tri-sec-butylborohydride. The preparation and characterization of these compounds are discussed. An improved synthesis for obtaining quantitative yields of (CO)3NiL [L = Me2NPF2, (Me2N)2PF, CH3NCH2CH2N(CH3)PF] is also described.
- Snow, Sarah S.,Jiang, De-Xiang,Parry, Robert W.
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p. 1460 - 1463
(2008/10/08)
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