TY - JOUR. T1 - Erratum. T2 - Poly(tertiary phosphines and arsines). 17. Poly(tertiary phosphines) containing terminal neomethyl groups as ligands in asymmetric homogeneous hydrogenation catalysts (Journal of Organic Chemistry (1979) 44, (3096)). AU - King, R. B.. AU - Bakos, J.. AU - Hoff, C. D.. AU - Markó, L.. PY - 1981. Y1 - 1981. UR - http://www.scopus.com/inward/record.url?scp=33845557797&partnerID=8YFLogxK. UR - http://www.scopus.com/inward/citedby.url?scp=33845557797&partnerID=8YFLogxK. M3 - Article. AN - SCOPUS:33845557797. VL - 46. SP - 2603. JO - Journal of Organic Chemistry. JF - Journal of Organic Chemistry. SN - 0022-3263. IS - 12. ER - ...
Phosphine is a fumigant used to protect stored commodities from infestation by pest insects, though high-level phosphine resistance in many insect species threatens the continued use of the fumigant. The mechanisms of toxicity and resistance are not clearly understood. In this study, the model organism, Caenorhabditis elegans, was employed to investigate the effects of phosphine on its proposed in vivo target, the mitochondrion. We found that phosphine rapidly perturbs mitochondrial morphology, inhibits oxidative respiration by 70%, and causes a severe drop in mitochondrial membrane potential ({Delta}{Psi}m) within 5 h of exposure. We then examined the phosphine-resistant strain of nematode, pre-33, to determine whether resistance was associated with any changes to mitochondrial physiology. Oxygen consumption was reduced by 70% in these mutant animals, which also had more mitochondrial genome copies than wild-type animals, a common response to reduced metabolic capacity. The mutant also had an ...
Phosphine resistance alleles might be expected to negatively affect energy demanding activities such as walking and flying, because of the inverse relationship between phosphine resistance and respiration. We used an activity monitoring system to quantify walking of Rhyzopertha dominica (F.) and a flight chamber to estimate their propensity for flight initiation. No significant difference in the duration of walking was observed between the strongly resistant, weakly resistant, and susceptible strains of R. dominica we tested, and females walked significantly more than males regardless of genotype. The walking activity monitor revealed no pattern of movement across the day and no particular time of peak activity despite reports of peak activity of R. dominica and Tribolium castaneum (Herbst) under field conditions during dawn and dusk. Flight initiation was significantly higher for all strains at 28°C and 55% relative humidity than at 25, 30, 32, and 35°C in the first 24 h of placing beetles in ...
An organopalladium complex containing ortho-metalated (S)-(1- (dimethylamino)ethyl)naphthalene as the chiral auxiliary has been used to promote the asymmetric hydrophosphination reactions between diphenylphosphine and (E)- or (Z)-diphenyl-1-propenylphosphine in high regio- and stereoselectivities under mild conditions. Hydrophosphination of (Z)-diphenyl-1-propenylphosphine with diphenylphosphine gave (S)-(-)-prophos as the major product. Using the same chiral metal template, the corresponding hydrophosphination reaction with (E)-diphenyl-1-propenylphosphine gave (R)-(+)-prophos predominantly. The hydrophosphination reactions generated the asymmetric diphosphines as bidentate chelates on the chiral naphthylamine palladium templates. The template products obtained undergo cis-trans isomerization in solution to form an equilibrium mixture of regioisomers. X-ray analysis of the major template products obtained from the hydrophosphination of (Z)-diphenyl-1-propenylphosphine reveals that the two ...
Karsch, Hans Heinz, Bienlein, F., Rupprich, T., Uhlig, F., Herrmann, Eckhard und Scheer, Manfred (1996) Tris(trimethylsilyl)phosphine, alkylbis(trimethylsilyl)phosphines, Bis(alkyl)(trimethylsilyl)phosphines, sodium bis(trimethylsilyl)phosphide, potassium bis(trimethylsilyl)phosphide - P(SiMe3)3, RP(SiMe3)2, NaP(SiMe3)2, KP(SiMe3)2. In: Karsch, Hans Heinz und Herrmann, Wolfgang A. und Brauer, Georg, (eds.) Synthetic methods of organometallic and inorganic chemistry: Phosphorus, Arsenic, Antimony, and Bismuth. Band 3. Thieme, Stuttgart, S. 58-65. ISBN 3-13-103041-0; 0-86577-654-7. Im Publikationsserver gibt es leider keinen Volltext zu diesem Eintrag. ...
There are no studies available for the determination of toxicokinetics or dermal absorption. Diphenyl(2,4,6 -trimethylbenzoyl)phosphine oxide is a powder with a molecular weight of 348 g/mol and a very low vapour pressure of 3x10e6Pa at 20 °C. In agreement with its logPow of 3.1, only 12mg can be dissolved in one liter of water. Due to its low vapour pressure, exposure to vapor is unlikely. The combination of a molecular weight below 500g/mol and moderate lipophilicity (logPoW between 1 and 4) favor oral as well as dermal uptake. Though acute dermal and oral toxicity tests did not show signs of systemic toxicity, sensitization was observed, hinting to dermal uptake of at least small amounts. In several repeated dose oral toxicity studies damage of testes, liver and kidneys was observed. From the logPoW below 4 it is expected, that the substance does not bioaccumulate. This is confirmed by the repeated dose studies. For the 28day and 90day study almost the same doses were used, which showed ...
Phosphine oxide, diphenyl(3-methylbutyl)- | C17H21OP | CID 206259 - structure, chemical names, physical and chemical properties, classification, patents, literature, biological activities, safety/hazards/toxicity information, supplier lists, and more.
A family of brightly luminescent dinuclear complexes of [Cu(μ2-X)(N^N)]2 type (X = I or SCN) has been synthesized in 76-90% yields by the reaction of bis(2-pyridyl)phosphine oxides (N^N) with the corresponding Cu(i) salts. The X-ray diffraction study reveals that the Cu2I2 core of the [Cu(μ2-I)(N^N)]2 comple
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Lesser Grain Borer : The Lesser Grain Borer is a small black or dark brown beetle. The body is slender and cylindrical. The head is hidden under the prothorax which is...
Phosphine ligands are also π-acceptors. Their π-acidity arises from overlap of P-C σ* anti-bonding orbitals with filled metal orbitals. Aryl- and fluorophosphines are stronger π-acceptors than alkylphosphines. Trifluorophosphine (PF3) is a strong π-acid with bonding properties akin to those of the carbonyl ligand.[6] In early work, phosphine ligands were thought to utilize 3d orbitals to form M-P pi-bonding, but it is now accepted that d-orbitals on phosphorus are not involved in bonding.[7] The energy of the σ* orbitals is lower for phosphines with electronegative substituents, and for this reason phosphorus trifluoride is a particularly good π-acceptor.[8] ...
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TY - JOUR. T1 - Facile, catalytic dehydrocoupling of phosphines using β-diketiminate iron(II) complexes. AU - King, Andrew K.. AU - Buchard, Antoine. AU - Mahon, Mary F.. AU - Webster, Ruth L.. PY - 2015/11/2. Y1 - 2015/11/2. N2 - Catalytic dehydrocoupling of primary and secondary phosphines has been achieved for the first time using an iron pre-catalyst. The reaction proceeds under mild reaction conditions and is successful with a range of diarylphosphines. A proton acceptor is not needed for the transformation to take place, but addition of 1-hexene does allow for turnover at 50 °C. The catalytic system developed also facilitates the dehydrocoupling of phenylphosphane and dicyclohexylphosphane. A change in solvent switches off dehydrocoupling to allow hydrophosphination of alkenes.. AB - Catalytic dehydrocoupling of primary and secondary phosphines has been achieved for the first time using an iron pre-catalyst. The reaction proceeds under mild reaction conditions and is successful with a ...
Find quality suppliers and manufacturers of 787618-22-8(Phosphine,[2,6-bis(1-methylethoxy)[1,1-biphenyl]-2-yl]dicyclohexyl-) for price inquiry. where to buy 787618-22-8(Phosphine,[2,6-bis(1-methylethoxy)[1,1-biphenyl]-2-yl]dicyclohexyl-).Also offer free database of 787618-22-8(Phosphine,[2,6-bis(1-methylethoxy)[1,1-biphenyl]-2-yl]dicyclohexyl-) including MSDS sheet(poisoning, toxicity, hazards and safety),chemical properties,Formula, density and structure, solution etc.
The general population may be exposed to very small amounts of phosphine in air, food or water. Workers who use this chemical may be exposed to higher levels. Exposure to phosphine can cause abdominal pain, nausea, and vomiting. High levels can cause weakness, bronchitis, pulmonary edema, shortness of breath, convulsions, and death. Phosphine has been found in at least 7 of the 1,585 National Priorities List sites identified by the Environmental Protection Agency (EPA).
CYTOP® 241 is a strong reducing agent and is used as a chemical intermediate. It readily undergoes free radical addition to olefins to generate sterically hindered tertiary phosphine ligands that are in turn useful in homogeneous catalysis. Its nucleophilic property makes it highly reactive towards alkylhalides such as benzyl or xylyl chlorides/bromides. In addition, it can be oxidized with either H2O2 or sulfur to yield either diisobutylphosphinic or dithiophosphinic acid and salts thereof.
Wear a self-contained breathing apparatus in pressure-demand, MSHA/NIOSH (approved or equivalent), and full protective gear. During a fire, irritating and highly toxic gases may be generated by thermal decomposition or combustion. Extinguishing media: Use agent most appropriate to extinguish fire. Do NOT get water inside containers. In case of fire use water spray, dry chemical, carbon dioxide, or appropriate foam ...
Reaction of two new phosphorus ylides Ph3PCHCOC10H7 (Y1) and Ph3PCHCOC4H3S (Y2) with mercury(II) halides and a previously reported ylide (p-tolyl)3PCHCOOCH2Ph (Y3) with CdCl2 in equimolar ratios using methanol as solvent yielded binuclear complexes of the type [(Y).HgX2]2 (Y=Y1 and Y2, X=Cl, Br and I) and a complex of [(Y3).HgCl2]2. The latter ylide reacts with Hg(NO3)2.H2O in the same solvent with equimolar ratios to give a polynuclear complex [Hg(Y3)(NO3)(μ-NO3)]n. Also, the reaction between ylides and AgNO3 in 1:2 molar ratios gave mononuclear complexes. Characterization of these products was carried out by elemental analysis, IR and multinuclear NMR techniques.
Reaction of bis(dicyclohexylphosphino)ethane dioxide with hydrogen peroxide leads to an extended crystalline network based on the formation of hydrogen bonds with the P [[double bond, length as m-dash]] O groups of the diphosphine dioxide. The structural motif of the network is characterized by X-ray diffractio...
0070]Specific examples of the optically active bisphosphine compound represented by the general formula (9) or (10) are, for example, 2,2-bis(diphenylphosphino)-1,1-binaphthyl, 2,2-bis[di(p-tolyl)phosphino]-1,1-binaphthyl, 2,2-bis[di(m-tolyl)phosphino]-1,1-binaphthyl, 2,2-bis[di(3,5-xylyl)phosphino]-1,1-binaphthyl, 2,2-bis[di(p-t-butylphenyl)phosphino]-1,1-binaphthyl, 2,2-bis[di(p-methoxyphenyl)phosphino]-1,1-binaphthyl, 2,2-bis[di(3,5-di-t-butyl-4-methoxyphenyl)phosphino]-1,1-binaphthyl, 2,2-bis[di(cyclopentyl)phosphino]-1,1-binaphthyl, 2,2-bis[di(cyclohexyl)phosphino]-1,1-binaphthyl, 2,2-bis(diphenylphosphino)-5,5,6,6,7,7,8,8-octahydro-1,1-binaphthyl- , 2,2-bis(di-p-tolylphosphino)-5,5,6,6,7,7,8,8-octahydro-1,1-binapht- hyl, 2,2-bis(di-m-tolylphosphino)-5,5,6,6,7,7,8,8-octahydro-1,1-bina- phthyl, 2,2-bis(di-3,5-xylylphosphino)-5,5,6,6,7,7,8,8-octahydro-1,1- -binaphthyl, 2,2-bis(di-p-t-butylphenylphosphino)-5,5,6,6,7,7,8,8-octahydro-1,1-- ...
article{6522cd05-413f-44ab-952b-a598c9530962, abstract = {Reaction of [Re-2(CO)(9)(NCMe)] with tri(2-thienyl)phosphine (PTh3) in refluxing cyclohexane affords three substituted dirhenium complexes: [Re-2(CO)(9)(PTh3)] (1), [Re-2(CO)(8)(NCMe)(PTh3)] (2), and [Re-2(CO)(8)(PTh3)(2)] (3). Complex 2 was also obtained from the room-temperature reaction of [Re-2(CO)(8)(NCMe)(2)] with PTh3 and is an unusual example in which the acetonitrile and phosphine ligands are coordinated to the same rhenium atom. Thermolysis of 1 and 3 in refluxing xylene affords [Re-2(CO)(8)(mu-PTh2)(mu-eta(1):kappa(1)-C4H3S)] (4) and [Re-2(CO)(7)(PTh3)(mu-PTh2)(mu-H)] (5), respectively, both resulting from carbon-phosphorus bond cleavage of a coordinated PTh3 ligand. Reaction of [Re-2(CO)10] and PTh3 in refluxing xylene gives a complex mixture of products. These products include 3-5, two further binuclear products, [Re-2(CO)(7)(PTh3)(mu-PTh2)(mu-eta(1):kappa(1)-C4H3S)] (6) and ...
The report generally describes tris-(4-methoxyphenyl)-phosphine, examines its uses, production methods, patents. Tris-(4-methoxyphenyl)-phosphine market
In organophosphorus chemistry, an aminophosphine is a compound with the formula R2−nP(NR2)n where R = H or an organic substituent, and n = 0, 1, 2. At one extreme, the parent H2PNH2 is lightly studied and fragile, but at the other extreme tris(dimethylamino)phosphine (P(NMe2)3) is commonly available. Intermediate members are known, such as Ph2PN(H)Ph. These compounds are typically colorless and reactive toward oxygen. They have pyramidal geometry at phosphorus. Typical aminophosphines undergo many of the reactions of tertiary phosphines: (i) oxidation to the oxide, (ii) P-alkylation (e.g. by methyl iodide) to the phosphonium cation, and (iii) coordination to soft metal electrophiles. Aminophosphines are characteristically prepared by treatment of a chlorophosphine with a primary or secondary amine. Illustrative is the reaction of chlorodiphenylphosphine and diethylamine: Ph2PCl + 2 HNEt2 → Ph2PNEt2 + [H2NEt2]Cl The P-N bond is susceptible to alcoholysis: Ph2PNEt2 + ROH → Ph2POR + HNEt2 The ...
CYTOP® 266 has been used to generate sterically hindered tertiary alkylphosphines which are, in turn, useful phosphine ligands for homogeneous catalysis. These ligands have been used in palladium catalyzed carbonylation and Suzuki-Miyaura cross-coupling reactions as well as the preparation of chiral organic compounds.
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Artur » Lista över publikationer » Syntheses and applications of chirally pure phosphine ligands from the natural lignan hydroxymataresinol ...
In this paper, four diiron toluene-3,4-dithiolate complexes with phosphine ligands were synthesized and characterized. Treatment of complex [Fe2(CO)6{μ
In the definitive test 128.11 mg of the test item was weighed into a glass flask (analytical balance SBC22, Scaltec) [SOP/W/7] and quantitatively transferred into a glass flask of 2 L capacity by multiple washing with test medium. The stock mixture of total volume of 1280 mL was heterogeneous with visible not dissolved parts of the test item. Therefore, the stock mixture was heated for 2 hours at 50oC in a water bath and then sonicated for 30 min (ultrasonic bath, Sonic-10, Polsonic [SOP/W/78]). The non-dissolved part of the mixture was separated by filtration thorough a conditioned nitrocellulose membrane filter (filter type HAWG, 0.45 µm pores, Millipore) [SOP/W/37]. The filtrate was a homogeneous and transparent solution and was used as the highest test concentration. The lower test concentrations were prepared by sequential dilutions with the test medium in a ratio 1 : 1, volume per volume (as given in Table 1). The generated solutions were treatments named: an undiluted filtrate of a ...
[1,1-Bis(diphenylphosphino)ferrocene]dichloropalladium(II) 72287-26-4 NMR spectrum, [1,1-Bis(diphenylphosphino)ferrocene]dichloropalladium(II) H-NMR spectral analysis, [1,1-Bis(diphenylphosphino)ferrocene]dichloropalladium(II) C-NMR spectral analysis ect.
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Shangyu Catsyn Co., Ltd. Cas 220114-03-4,Dichloro{(S)-(-)-2,2-bis[di(3,5-xylyl)phosphino]-1,1-binaphthyl}[(1S,2S)-(-)-1,2-diphenylethylenediamine]ruthenium(II), RuCl2[(S)-xylbinap][(S,S)-dpen];DICHLORO[(S)-(-)-2,2-BIS[DI(3,5-XYLYL)PHOSPHINO]-1,1-BINAPHTHYL][(1S,2S)-(-)-1,2-DIPHENYLETHYLENEDIAMINE]RUTHENIUM(II);RUCL2[(S)-(DM-BINAP)][(S,S)-DPEN];RUCL2[(S)-XYLBINAP][(S,S)-DPEN];Dichloro{(S)-(-)-2,2-bis[di(3,5-xylyl)phosphino]-1,1-binaphthyl}[(1S,2S)-(-)-1,2-diphenylethylenediamine]ruthenium(II), ?RuCl2[(S)-xylbinap][(S,S)-dpen];SC10173.
Sodium phosphide is a black solid. It is ionic. There are several other sodium phosphides that do not have the formula Na3P. It reacts with acids to make phosphine gas. It is a reducing agent. ...
Diphosphine ligands have been widely used in organometallic chemistry and catalysis.1 By incorporation of functional units such as metallomacrocycles, the resulting functionalized diphosphines could exhibit unusual properties or binding behavior. In this study, we prepared several examples of ruthenium porphyrin phosphine complexes [RuII(Por)(dppm)2] (1; Por = TTP, 4-MeO-TPP, F20-TPP; dppm = bis(diphenylphosphino)methane) by a similar method to that previously reported for their congeners.2 Reaction of complexes 1 with a number of metal ...
Description: The reaction of 2-[(diphenylphosphino)methyl]-6-methylpyridine (PN) with Os3(CO)12-n(MeCN)n [where n = 0 (1), 1 (2), 2 (3)] has been investigated. Os3(CO)12 reacts with PN in the presence of Me3NO to afford the clusters Os3(CO)11(1-PN) (4) and 1,2-Os3(CO)10(1-PN)2 (5). X-ray diffraction analyses confirm the equatorial coordination of the phosphine(s) in 4 and 5, with the two phosphines in the latter cluster exhibiting a 1,2-trans orientation about the Os-Os vector that contains the two ligands. Treatment of the MeCN-substituted cluster Os3(CO)11(MeCN) and PN (1:1 ratio) in CH2Cl2 gives clusters 4 and 5, in addition to HOs3(η1-Cl)(CO)10(1-PN) (6) as a result of competitive activation of the reaction solvent. Cluster 6 contains 48e- and the diffraction structure reveals the presence of axial chloride and equatorial phosphine ligands which are located on adjacent osmium atoms. The bridging hydride ligand in 6 spans the Cl,P-substituted Os-Os vector. The reaction of Os3(CO)10(MeCN)2 ...
The immobilization of the dinuclear platinum(II) sulfido complex [Pt₂(μ-S)₂ (PPh₃)₄] on solid supports has been investigated. Reaction with haloalkyl functionalized polymers [Merrifields resin (chloromethylated polystyrene), chloropropyl silica, chloropropyl controlled pore glass, and bromopropyl polysiloxane] gives complexes immobilized through alkylation of one of the sulfide ligands, forming a μ-thiolate ligand acting as an anchor to the polymer support, akin to well-established reactions of [Pt₂(μ-S)₂(PPh₃)₄] with molecular alkylating agents. The model complex [Pt₂(μ-S)(μ-SCH₂SiMe₃)(PPh₃)₄]PF₆ was prepared as the first molecular silicon-containing derivative of [Pt₂(μ-S)₂(PPh₃)₄] and was fully characterized by NMR spectroscopy, electrospray ionization-mass spectrometry, and single-crystal X-ray diffraction. Immobilization of [Pt₂(μ-S)₂(PPh₃)₄] by phosphine exchange reactions was also achieved using commercial polystyrene-grafted ...
[65 Pages Report] Check for Discount on tris(diethylamino)phosphine Global Market and Forecast Research report by ChemReport. DescriptionWe provide independent and unbiased information on manufacturers, prices, production...
The substitution of trimethylphosphine for triphenylphosphine in {eta}{sup 5}-cyclopentadienyl-bis-triphenylphosphinecobalt(I), 1, to form {eta}{sup 5}-cyclopentadienyltrimethylphosphinetriphenylphosphinecobalt(I) was studied at -60°C in an NMR spectrometer. Kinetic measurements show the process to be first order in 1 and zero order in PMe{sub 3}; added PPh{sub 3} strongly inhibits the reaction rate. This information indicates the reaction proceeds by rapid reversible phosphine dissociation through the unsaturated CpCo(PPh{sub 3}) intermediate. The rate for generation of that intermediate, k{sub 1}, is 1.15 x 10{sup -3} sec{sup -1} while the ratio of rate constant k{sub 2} (for conversion of intermediate to products) to k{sub -1} (return to starting materials) is 4 at -60°C. Possible structures for CpCo(L) are discussed in light of recent indications that the linear structure has an open-shell electronic configuration.
1810-7805 - Calibration Gas Phosphine 5ppm Balance Nitrogen 34 Liter GAL C-10 Inlet Cylinder (Made by Portagas) (No RFID tag)
3878-45-3 - VYNGFCUGSYEOOZ-UHFFFAOYSA-N - Phosphine sulfide, triphenyl- - Similar structures search, synonyms, formulas, resource links, and other chemical information.
Talk at 51st International Symposium of AVS, Anaheim, CA, 11/16/2004. "STM study of phosphine adsorption on Si(111)-7x7 surfaces," presented by J.-Y.Ji and T-C Shen.. ...
[(2Z)-2-[(3S,5R)-3,5-Bis[[(1,1-dimethylethyl)dimethylsilyl]oxy]-2-methylenecyclohexylidene]ethyl]diphenylphosphine Oxide - Gentaur.com - Product info
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Highly efficient methods for synthetic modifications of the natural lignan hydroxymatairesinol into chiral diphosphines similar to DIOP were developed. Catalytic activity and induction of enantioselectivity for the prepd. phosphines were evaluated in rhodium catalyzed hydrogenations of different functionalized alkenes. High catalytic activities were obsd. with low catalyst loading at atm. pressure. The phosphines showed moderate to high enantioselectivity depending on the substrate used. Hydrogenation of 1-​acetamidostyrene gave 84​% ee of the S-​enantiomer. ...
The anti-contractile effect of perivascular adipose tissue (PVAT) is an important mechanism in the modulation of vascular tone in peripheral arteries. Recent evidence has implicated the XE991-sensitive voltage-gated Kv (KCNQ) channels in the regulation of arterial tone by PVAT. However, until now the in vivo pharmacology of the involved vascular Kv channels with regard to XE991 remains undetermined, since XE991 effects may involve Ca2+ activated BKCa channels and/or voltage-dependent Kv1.5 channels sensitive to diphenyl phosphine oxide-1 (DPO-1). In this study, we tested whether Kv1.5 channels are involved in the control of mesenteric arterial tone and its regulation by PVAT. Our study was also aimed at extending our current knowledge on the in situ vascular pharmacology of DPO-1 and XE991 regarding Kv1.5 and BKCa channels, in helping to identify the nature of K+ channels that could contribute to PVAT-mediated relaxation. XE991 at 30 µM reduced the anti-contractile response of PVAT, but had no effects
TY - JOUR. T1 - Organolanthanide-catalyzed synthesis of phosphine-terminated polyethylenes. AU - Kawaoka, Amber M.. AU - Marks, Tobin J. PY - 2004/10/13. Y1 - 2004/10/13. N2 - Organolanthanide-mediated hydrophosphination and ethylene polymerization are coupled in a catalytic cycle to produce diphenylphosphine-terminated polyethylenes. The resulting polymers were characterized by 1H, 13C, and 31P NMR, GPC, and DSC and compared spectroscopically to the model compound, 1-eicosyldiphenylphosphine oxide. High activities (107 g polymer/(mol Ln·atm ethylene·h)) and narrow polydispersities were observed in the polymerization/chain transfer process. Polyethylene molecular weights were found to be inversely proportional to diphenylphosphine concentration, supporting a chain transfer mechanism. The present discovery represents the first case in which an electron-rich phosphine functions efficiently as a chain transfer agent in a single-site fn/d0-mediated olefin polymerization process.. AB - ...
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EN] The purpose of this review article is to illustrate synthetic aspects of functionalized phosphorus derivatives containing an oximo moiety at the beta-position. First section will be focused on the synthesis of phosphine oxides, phosphonates or phosphonium salts containing an oxime group. The synthesis of these derivatives comprises the carbon-phosphorus single bond construction by reaction of haloximes with phosphorus derivatives, nucleophilic addition of phosphorus reagents to carbonyl compounds, or nucleophilic addition of phosphorus reagents to nitro olefins. This section will also concentrate on the most practical routes for the synthesis of the target compounds, through carbon-nitrogen double bond formation, which are as follows: condensation processes of carbonyl compounds and hydroxylamine derivatives or addition of hydroxylamines to allenes or alkynes. The preparative use of beta-oximo phosphorus derivatives as synthetic intermediates will be discussed in a second section, comprising ...
628 Gold(I) phosphine derivatives have previously attracted interest as potential antitumour agents but hepatotoxicity was encountered during preclinical development. A series of bidentate pyridyl phosphine gold(I) and silver(I) complexes were synthesised covering a range of lipophilic/hydrophilic properties. Previously we reported that their lipophilicity greatly affects cellular uptake and cytotoxicity in a CH1 cell line. Herein we examined their in vitro uptake and cytotoxicity in a panel of human ovarian tumor cell lines and isolated hepatocytes. Sulforhodamine B assay and lactate dehydrogenase release assay were used to determine tumor cell growth inhibition and hepatocyte viability. Gold content was analyzed by inductively coupled plasma mass spectrometry. The in vitro cytotoxicity of bidentate pyridyl phosphine complexes to isolated hepatocytes and ovarian tumor cell lines correlated with their lipophilicity and rate of gold uptake. The 3- and 4-pyridyl derivatives showed less ...
Engineering the electronic properties of transition metal phosphides has shown great effectiveness in improving their intrinsic catalytic activity for the hydrogen evolution reaction (HER) in water splitting applications. Herein, we report for the first time, the creation of Fe vacancies as an approach to modulate the electronic structure of iron phosphide (FeP). The Fe vacancies were produced by chemical leaching of Mg that was introduced into FeP as "sacrificial dopant". The obtained Fe-vacancy-rich FeP nanoparticulate films, which were deposited on Ti foil, show excellent HER activity compared to pristine FeP and Mg-doped FeP, achieving a current density of 10 mAcm(-2) at overpotentials of 108 mV in 1 m KOH and 65 mV in 0.5 m H2SO4, with a near-100% Faradaic efficiency. Our theoretical and experimental analyses reveal that the improved HER activity originates from the presence of Fe vacancies, which lead to a synergistic modulation of the structural and electronic properties that result in a ...