- Synthesis of 1,3,5,2λ5-triazaphosphinines by intramolecular cyclisation of (N-cyanophosphorimidoyl)guanidines and diguanidinophosphonium chlorides
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The sodium phosphonium diylide Na[Ph2P(NCN)2] (3) - the first example of a stabilised phosphonium diylide - was synthesised by treatment of sodium diphenylphosphide with 2 equiv. of cyanic azide. Compound 3 reacted with alkyl- and ar
- Inguimbert, Nicolas,Jaeger, Lothar,Taillefer, Marc,Biedermann, Matthias,Cristau, Henri-Jean
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- Synthesis, coordination and extraction properties of 2,3-bis(diphenylphosphoryl)pyridine toward f-block elements
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2,3-Bis(diphenylphosphoryl)pyridine, a novel N,O-donor bidentate organophosphorus ligand, can serve as an efficient extractant for recovery of f-block elements from nitric acid solutions.
- Artyushin, Oleg I.,Brel, Valery K.,Karandashev, Vasilii K.,Turanov, Aleksandr N.,Vologzhanina, Anna V.
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- Migration insertion polymerization (MIP) of cyclopentadienyldicarbonyldiphenylphosphinopropyliron (FpP): A new concept for main chain metal-containing polymers (MCPs)
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We report a conceptually new polymerization technique termed migration insertion polymerization (MIP) for main chain metal-containing polymer (MCP) synthesis. Cyclopentadienyldicarbonyldiphenylphosphinopropyliron (FpP) is synthesized and polymerized via M
- Wang, Xiaosong,Cao, Kai,Liu, Yibo,Tsang, Brian,Liew, Sean
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- Synthesis and solution behaviour of metal-carbonyl amphiphiles with an Fp (CpFe(CO)2) junction
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Metallo-amphiphilic macromolecules with an iron-carbonyl junction (PEGPPh2-FpR, PEGPPh2: polyethylene glycol diphenyl phosphine, Mn, PEG = 550 or 2000 g/mol; R = octadecyl or hexyl; Fp = CpFe(CO)2) are synthesiz
- Murshid, Nimer,El-Temtamy, Abdelrahman,Wang, Xiaosong
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- Experimental and theoretical studies of highly emissive dinuclear Cu(i) halide complexes with delayed fluorescence
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A series of luminescent homo-dinuclear Cu(i) halide complexes, [PPh2PAr2Cu(μ-X)2CuPPh2PAr2] (X = I (1), Br (2), Cl (3)) (PPh2PAr2 = (1-bis(2-methylphenyl)phosphino-2-diphenylphos
- Kang, Liju,Chen, Jin,Teng, Teng,Chen, Xu-Lin,Yu, Rongmin,Lu, Can-Zhong
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- Reductive conversion of phosphoryl P(O) compounds to trivalent organophosphines R3P
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By introducing trimethylsilyl chloride (TMSCl), the pentavalent phosphoryl P(V) compounds such as triphenylphosphine oxides, secondary phosphine oxides etc., were readily converted to the corresponding R2P(OTMS) intermediates, that can further react efficiently with an electrophile R'X or with a nucleophile R'Li to produce the corresponding trivalent phosphines R2PR’. Chiral phosphines could also be obtained stereospecifically by this strategy.
- Zhang, Jian-Qiu,Han, Li-Biao
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supporting information
(2021/02/20)
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- Ready Approach to Organophosphines from ArCl via Selective Cleavage of C-P Bonds by Sodium
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The preparation, application, and reaction mechanism of sodium phosphide R2PNa and other alkali metal phosphides R2PM (M = Li and K) have been studied. R2PNa could be prepared, accurately and selectively, via the reactions of SD (sodium finely dispersed in mineral oil) with phosphinites R2POR′ and chlorophosphines R2PCl. R2PNa could also be prepared from triarylphosphines and diarylphosphines via the selective cleavage of C-P bonds. Na was superior to Li and K for these reactions. R2PNa reacted with a variety of ArCl to efficiently produce R2PAr. ArCl is superior to ArBr and ArI since they only gave low yields of the products. In addition, Ph2PNa is superior to Ph2PLi and Ph2PK since Ph2PLi did not produce the coupling product with PhCl, while Ph2PK only gave a low yield of the product. An electron-withdrawing group on the benzene ring of ArCl greatly accelerated the reactions with R2PNa, while an alkyl group reduced the reactivity. Vinyl chloride and alkyl chlorides RCl also reacted efficiently. While t-BuCl did not produce the corresponding product, admantyl halides could give the corresponding phosphine in high yields. A wide range of phosphines were prepared by this method from the corresponding chlorides. Unsymmetric phosphines could also be conveniently generated in one pot starting from Ph3P. Chiral phosphines were also obtained in good yields from the reactions of menthyl chlorides with R2PNa. Possible mechanistic pathways were given for the reductive cleavage of R3P by sodium generating R2PNa and the substitution reactions of R2PNa with ArCl generating R2PAr.
- Ye, Jingjing,Zhang, Jian-Qiu,Saga, Yuta,Onozawa, Shunya,Kobayashi, Shu,Sato, Kazuhiko,Fukaya, Norihisa,Han, Li-Biao
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supporting information
p. 2682 - 2694
(2020/07/30)
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- A Bioinspired Multicomponent Catalytic System for Converting Carbon Dioxide into Methanol Autocatalytically
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Nature utilizes multicomponent catalyst systems to convert simple, abundant starting materials into complex molecules that are essential for life. In contrast, synthetic chemical transformations rarely adopt this strategy because it is difficult to replicate the sophisticated supramolecular assemblies used by biology for active-site separation and substrate trafficking. Here, we describe a method for multicomponent catalyst separation that involves encapsulating transition-metal complexes in nanoporous materials called metal-organic frameworks. The multicomponent catalyst system was highly active for converting hydrogen and carbon dioxide to methanol, and it could be formulated to be readily recyclable. Moreover, we uncovered an autocatalytic feature that was possible only when we utilized the multicomponent catalyst strategy. These results open avenues for obtaining fuel from abundant and renewable resources. Methanol is a promising renewable fuel that can be adapted to the current liquid fuel infrastructure. It can be produced from hydrogen and carbon dioxide, mitigating greenhouse gas emissions and storing hydrogen in the process. However, the industrial production of methanol through this hydrogenation reaction currently requires elevated temperatures and pressures and can produce significant amounts of unwanted byproducts. Here, we employ a bioinspired tandem catalytic system to efficiently hydrogenate carbon dioxide to methanol selectively at low temperatures. We achieved superior performance by eliminating catalyst incompatibility through encapsulating at least one of the catalysts involved in the tandem process in nanoporous materials called metal-organic frameworks. In the long term, this method could be applied to other tandem catalytic processes, allowing more efficient access to alternative fuels, commodity chemicals, and valuable pharmaceutical products. Tsung and co-workers describe a three-component tandem catalytic process for the hydrogenation of carbon dioxide to methanol. The bioinspired process is enabled by encapsulation of at least one of the two ruthenium-based catalysts required in the metal-organic framework (MOF) UiO-66. The reaction was found to have an autocatalytic feature that enables the reaction to be carried out without superstoichiometric additives. Encapsulating both ruthenium-based catalysts in the MOF allowed the catalyst to be recycled.
- Rayder, Thomas M.,Adillon, Enric H.,Byers, Jeffery A.,Tsung, Chia-Kuang
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supporting information
p. 1742 - 1754
(2020/05/25)
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- Hard-and-soft phosphinoxide receptors for f-element binding: structure and photophysical properties of europium(iii) complexes
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New phosphinoyl-containing tetradentate heterocycles preorganised for metal ion binding were designed and prepared in high yields. The X-ray structures of two allied phosphinoyl-bearing 2,2′-bipyridyl and phenanthroline ligands, as well as closely related structures of 2,6-bis(diphenylphosphinoyl)pyridine and 9-(diphenylphosphinoyl)-1,10-phenanthroline-2-one, are reported. Complexes of nitrates of several lanthanides and trifluoroacetate of Eu(iii) with two phosphinoyl-bearing 2,2′-bipyridyl and phenanthroline ligands were isolated and characterised. The first structures of lanthanide complexes with phosphinoyl-bearing 2,2′-bipyridyl and phenanthroline ligands are reported. The nature of the counter-ion is crucial for the coordination environment of the metal ion. The photophysical properties of the complexes differring in both the nature of the ligand and counter-ion were investigated. The photophysical properties of the complexes are strongly ligand- and counter-ion-dependent. Absorbance and luminescence excitation spectra of complexes showed main peaks in the UV range which correspond to the absorption of light by the ligand and these are ligand-dependent. Luminescence spectra of complexes show typical europium emission in the red region with a high quantum yield, which orresponds to the transitions5D0→7FJ (J = 0-6). The value of deviation of the components of5D0 →7F2 and5D0 →7F1 transitions from the inversion centre shows a larger dependence on the counter-ion than on the nature of the ligand. The value of the luminescence quantum yield is larger for europium complexes with 2,2′-bipyridyl-based ligands and NO3 counter-ions than for complexes with phenanthroline-based ligands and NO3 counter-ions. A low dependence of the luminescence lifetime of Eu complexes on the nature of the ligand has been demonstrated: values in the solid state were in the range 1.1-2.0 ms.
- Borisova, Nataliya E.,Kharcheva, Anastasia V.,Patsaeva, Svetlana V.,Korotkov, Leonid A.,Bakaev, Sergey,Reshetova, Marina D.,Lyssenko, Konstantin A.,Belova, Elena V.,Myasoedov, Boris F.
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p. 2238 - 2248
(2017/02/26)
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- Short wave ultraviolet excitation of the high efficiency of the rare earth complex light-emitting material
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The invention discloses a rare earth complex luminescent material based on aromatic heterocyclic carboxylic class three-tooth anionic ligands and preparing method and application thereof. The general formula of rare earth complex is Ln (L)3. The L is 2-ca
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Paragraph 0027-0030
(2018/01/05)
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- Synthesis, cyclization, and migration insertion oligomerization of CpFe(CO)2(CH2)3PPh2 in solution
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Cyclopentadienyldicarbonyl[(diphenylphosphino)propyl]iron (CpFe(CO) 2(CH2)3PPh2, FpP), containing both Fp and phosphine groups, was synthesized as a difunctional monomer for migration insertion polymerization (M
- Cao, Kai,Tsang, Brian,Liu, Yibo,Chelladural, Daniel,Power, William P.,Wang, Xiaosong
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p. 531 - 539
(2014/02/14)
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- NOVEL COMPOUND AND ORGANIC DEVICE EMPLOYING SAME
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The compounds represented by the following general formula have excellent properties as a charge transport material. In the formula, R1 to R3 represent a substituent, n1 and n2 indicate an integer of from 0 to 5, n3 indicates an inte
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Paragraph 0105; 0106
(2014/06/24)
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- NAPHTHENIC HYDROCARBON ADDITIVES FOR DIARYL PHOSPHIDE SALT FORMATION
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The invention relates to the use of polycyclic aromatic hydrocarbons (PAHs) such as naphthalene and its alkyl, aryl, or heteroatom substituted analogs, that act as catalysts in the presence of an alkali metal (Li, K, Na) for the reduction of electron-deficient and electron-rich triaryl phosphines to their corresponding alkali metal diaryl phosphide salts. The process is also useful for the catalysis of triaryl phosphine chalcogen adducts such as the sulfides, oxides, and selenides, diaryl(halo)phosphines, triaryl phosphine-borane adducts, and tetra-aryl bis(phosphines) that can also be reduced to their corresponding alkali metal diaryl phosphide salts. The invention also relates to small molecule PAHs and polymer tethered PAHs naphthenics.
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Page/Page column 10
(2010/09/18)
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- METHOD FOR GENERATING ALKALI METAL PHOSPHIDES THROUGH REDUCTION OF TRI-SUBSTITUTED PHOSPHINES WITH ALKALI METAL POROUS OXIDE COMPOSITIONS
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Alkali metal phosphides are useful intermediates for the synthesis of a variety of phosphine derivatives. Many of these phosphine derivatives are important industrial compounds with applications as synthetic intermediates or as ligands in a variety of homogeneous and heterogeneous synthetic processes. Alkali metal diarylphosphides in particular have been used in the synthesis of many phosphine ligands of importance. The invention relates to methods for generating and using alkali metal phosphides by reduction of the phosphorus sigma bonds of tri-substituted phosphorus derivatives with Group I metal/porous oxide compositions. Formula (I).
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Page/Page column 16
(2008/12/08)
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- LITHIUM P-DIARYLPHOSPHINOBENZENESULFONATES, PROCESS FOR PREPARATION OF THE SAME AND USE THEREOF
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Lithium p-diarylphosphinobenzenesulfonates represented by the general formula (I) wherein R1 and R2 are each optionally substituted aryl; a process for preparing the same; a group VIII metal complex comprising a group VIII metal compound and the above lithium p-diarylphosphinobenzenesulfonate coordinating thereto and a process for hydroformylation with the complex. Hydroformylation with the complex permits easy and industrially advantageous production of aldehydes.
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- BISPHOSPHINE, PROCESS FOR PRODUCING THE SAME, AND USE THEREOF
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Bisphosphines represented by the general formula (I) wherein Ar1 and Ar2 each represents an arylene group which may be substituted; R1 and R2 each represents an alkyl group which may be substituted, or an aryl group which may be substituted, or R1 and R2 may combinedly form a ring together with the phosphorus atom bonded thereto; R3 and R4 each represents hydrogen atom or an alkyl group; and the carbon atoms each having R3 and R4 are bonded in positions ortho to the oxygen atom bonded to Ar1 and Ar2: process for production thereof; Group VIII metal complexes comprising said bisphosphines; and process for producing aldehydes, which comprises, on hydroformylation of ethylenically unsaturated compounds with carbon monoxide and hydrogen, using said Group VIII metal complexes.The hydroformylation of ethylenically unsaturated compounds according to the present invention can produce n-aldehydes at higher reaction rate and industrially more advantageously than with catalysts comprising conventional phosphines, while suppressing side reactions such as hydrogenation and isomerization.
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- Preparation of substituted phosphide salts
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Substituted sodium salts of phosphides are prepared by reacting a triarylphosphine with sodium in an aliphatic amine or diamine as a solvent or co-solvent. The resultant phosphides may be further treated with appropriate halides to produce unsymmetrical phosphines.
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- Sterically hindered iminophosphorane complexes of vanadium, iron, cobalt and nickel: a synthetic, structural and catalytic study
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Bis(aryliminophosphoranyl)alkanes L1 = (CH2)n(R12P=NR2)2 (n = 1 or 2, R1 = Ph or Me, R2 = Ph, C6H2Me3-2,4,6 or C6H3Pri2-2,6) reacted with cobalt and nickel dihalides to give chelate complex
- Al-Benna, Sarah,Sarsfield, Mark J.,Thornton-Pett, Mark,Ormsby, Daniel L.,Maddox, Peter J.,Bres, Philippe,Bochmann, Manfred
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p. 4247 - 4257
(2007/10/03)
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- Binuclear complexes with ligands based on the 2,6-bis(diphenylphosphinomethyl)benzene framework. Syntheses and crystal structures of [Ir2Cl2(μ-CO){2,6-(Ph2PH2) 2C6H3S}2
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The new binucleating phosphinothiolate proligand 2,6-(Ph2PCH2)C6H4SH (L3H) was prepared from bromo-2,6-dimethylbenzene in a 4 step synthesis. Reaction with [IrCl(CO)(PPh3)2] in MeCN gave th
- Dilworth, Jonathan R.,Zheng, Yifan,Griffiths, D. Vaughan
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p. 1877 - 1881
(2007/10/03)
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- Synthesis of cycloalkyldiarylphosophines
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Phosphines having two aryl groups and one alkyl-substituted cycloalkyl group bonded to a phosphorus atom are formed by reacting an alkali metal diarylphosphide with a monoalkyl- or polyalkyl-substituted cycloalkyl mesylate or tosylate in which an alkyl gr
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- Synthesis of cycloalkyldiarylphosphines
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By reacting certain partially sterically-hindered chloro-substituted cycloalkanes with sodium and/or potassium diarylphosphides in an ether reaction medium, not only are useful cycloalkyldiarylphosphines produced, but in addition the chloro-substituted cycloalkane does not undergo any appreciable reaction with the coproduced aryl sodium and/or aryl potassium as it is formed. Moreover, the process makes it possible to avoid or at least to greatly reduce interaction with or cleavage of cyclic ether reaction media such as tetrahydrofuran. Thus the process makes possible improvements both in yield and quality of the cycloalkyldiarylphosphite product. A two-stage process conducted in an ether reaction medium is also described. In the first stage the sodium and/or potassium diarylphosphine reactant is produced by reaction between sodium and/or potassium and triarylphosphine.
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- Synthesis of chiral organophosphorous ligands based on transformations of methyl 3,4-O-isopropylidene-L-threonate
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Chiral organophosphorous compounds which are or interest as ligands for metallocomplex catalysts for enantioselective transformations were synthesized from methyl 3,4-O-isopropylidene-L-threonate.
- Tolstikov,Amosov,Tolstikova,Khlebnikova,Zakharova
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p. 381 - 383
(2007/10/03)
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- Electron Transfer in the Reactions of Geminal Dihalides with Ph2P(-). Evidence for the Formation of a Carbene Intermediate from a Radical Precursor
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The reactions of two sterically hindered geminal dihalides, 6,6-dichloro-5,5-dimethyl-1-hexene (5a) and 6,6-diiodo-5,5-dimethyl-1-hexene (5b), with Ph2P(-) have been found to involve a single electron transfer (SET) pathway.Since the corresponding monochl
- Ashby, E. C.,Deshpande, Abhay K.
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p. 7117 - 7124
(2007/10/03)
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- Preparations of chiral pyrrolidinebisphosphines bearing two different types of phosphino groups and their use in efficient catalytic asymmetric hydrogenation
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Chiral pyrrolidinebisphosphine ligands, (2S-cis)-BCPM and (2S-cis)-BCPP, bearing two different types of phosphino groups, a dicyclohexylphosphino group and a diphenylphosphino group, were designed and prepared on the basis of our design concept for developing highly efficient ligands. The validity of the concept was confirmed experimentally in the asymmetric hydrogenation of ketopantolactone using neutral rhodium(I) complexes of BCPM. BCPP, BPPM, and BCCP. The rhodium(I) complex of (2S-cis)-BCPM was found to be the most effective catalyst (substrate/catalyst >ca. 104, >90% ee (R)).
- Morimoto,Takahashi,Achiwa
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p. 481 - 488
(2007/10/02)
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- Investigation of the Purity of Alkali Metal Diphenylphosphides and Their Reactions with Organic Halides. Evidence for Single Electron Transfer
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For the first time the purity of lithium, sodium, and potassium diphenylphosphide, prepared by various methods, has been evaluated using (31)P NMR spectroscopy.A method was developed to prepare each of the phosphides in a high state of purity.Highly pure potassium diphenylphosphide was then allowed to react with p-iodotoluene in order to determine the effect of purity on the SRN1 nature of this reaction.The results were then compared with literature reports which used less pure KPPh2.The mechanism of reaction of alkyl halides with pure alkali metal diphenylphosphides, using the radical probes 6-halo-5,5-dimethyl-1-hexenes and 1-halo-2,2-dimethylhexanes, was investigated.The results provide the first evidence to support single electron transfer (SET) in the reaction of an alkali metal diphenylphosphide with an alkyl halide.SET was found to be the major reaction pathway in the reaction of hindered alkyl iodides (neopentyl type).On the other hand, SET was found to be a minor pathway in the reaction of the corresponding alkyl bromides and chlorides with PPh2(1-).There was no evidence found for SET in the reactions of unhindered alkyl halides with PPh2(1-) although SET participation cannot be rigorously excluded.
- Ashby, E. C.,Gurumurthy, R.,Ridlehuber, R. W.
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p. 5832 - 5837
(2007/10/02)
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- Preparation of ortho substituted diphenylphosphides
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Alkali metal di(2-alkoxyphenyl)phosphide is produced in good yield by reaction of alkali metal and the corresponding tri(2-alkoxyphenyl)-phosphine in liquid ammonia.
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- Preparation and Characterization of Cobalt(III) Complexes Containing 4,7-Diphenyl-4,7-diphosphadecane-1,10-diamine and 4,8-Diphenyl-4,8-diphosphaundecane-1,11-diamine, NH2(CH2)3P(C6H5)(CH2)nP(C6H5)(CH2)3NH2 (n=2,3)
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Twelve new cobalt(III) complexes of the types, cisα-p+ (L=2,4-pentanedionate (acac) and oxalate (ox) ions) (four complexes) and cisβ-p+ (eight complexes) were prepared and characterized by 1H NMR and absorption spectra, where rac(P)- and meso(P)-323NPPN denote rac(P)- and meso(P)-NH2(CH2)mP(C6H5)(CH2)nP(C6H5)(CH2)mNH2 with m=3 and n=2, and 333NPPN the ligand with m=3 and n=3.Reactivities of the complexes towards hydrochloric acid were examined and compared with those of the corresponding 222NPPN (m=2, n=2) and 232NPPN (m=2, n=3) complexes.All the cisα isomers yield the cisα-dichloro complexes, the 333NPPN and 222NPPN complexes being more reactive than the 232NPPN and 323NPPN complexes in which five- and six-membered chelate rings of NPPN are involved.For the cisβ isomers, the acac complexes afford +)>2+ except the rac(P)- and meso(P)-333NPPN complexes which give the trans-dichloro complexes, while all the ox complexes liberate the ox ion to yield the dichloro complex of the cisα, cisβ, or trans configuration.For both cisβ-acac and -ox isomers, the 222NPPN and 232NPPN complexes are more reactive than those of 323NPPN and 333NPPN, and the meso(P)-complexes are more reactive than the rac(P)-complexes.
- Kashiwabara, Kazuo,Jung, Minho,Fujita, Junnosuke
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p. 2372 - 2377
(2007/10/02)
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- ZUR KENNTNIS DES NATRIUMDIPHENYLPHOSPHINOFORMIATS Ph2PCOONa
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Ph2PCOONa 2, prepared from Ph2PNa and CO2, is readily hydrolyzed in protic media with formation of Ph2PH and CO2.Hydrolysis is much slower in NaOH and small quantities of Ph2P(O)O- and HCOO- are additionally formed.Reactions of 2 with RI in stoichiometrical amounts gave tertiary phosphines Ph2PR (R=Me, Et) while the phosphonium compound I resulted from 2 and MeI in excess.Ph2PCOOMe, Ph2PCOOSiMe3 or Ph2PCSSNa were obtained from 2 and (MeO)2SO2, Me3SiCl or CS2.Ph2P(O)ONa and Ph2P(S)SNa were isolated when 2 was reacted with O2 or S8 in benzene.
- Diemert, Klaus,Hahn, Thomas,Kuchen, Wilhelm
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p. 287 - 294
(2007/10/02)
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- Orbital control in the reductive cleavage of tris(methoxyphenyl)phosphines
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The character of the LUMO of (methoxyphenyl)phosphines determines the reductive cleavage of the C-P bond; a high LUMO energy prevents reduction whereas a small coefficient at the C-P carbon atom leads to a poor cleavage.
- Budzelaar, Peter H. M.,Doorn, Johannes A. van,Meijboom, Nico
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p. 253 - 254
(2007/10/02)
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