Search results for "phosphine"
showing 10 items of 618 documents
Morphology control in biphasic hybrid systems of semiconducting materials.
2015
Simple blends of inorganic nanocrystals and organic (semiconducting) polymers usually lead to macroscopic segregation. Thus, such blends typically exhibit inferior properties than expected. To overcome the problem of segregation, polymer coated nanocrystals (nanocomposites) have been developed. Such nanocomposites are highly miscible within the polymer matrix. In this Review, a summary of synthetic approaches to achieve stable nanocomposites in a semiconducting polymer matrix is presented. Furthermore, a theoretical background as well as an overview concerning morphology control of inorganic NCs in polymer matrices are provided. In addition, the morphologic behavior of highly anisotropic na…
Studien zum Vorgang der Wasserstoffübertragung 46. Zur kathodischen Spaltung von Alkyl- und Cycloalkyl(triphenyl)-phosphoniumsalzen; Abhängigkeit der…
1977
Die kathodische Spaltung von Methyl-, Butyl- und einiger Cycloalkyl(triphenyl)phosphoniumsalze wurde potentiostatisch und galvanostatisch durchgefuhrt. Beim Methyl(triphenyl)-phosphoniumsalz hangt die prozentuale Zusammensetzung der Spaltprodukte: Triphenylphosphin und Methyl(diphenyl)phosphin sowohl vom Potential als auch von der Temperatur ab, die sich ihrerseits wieder gegenseitig beeinflussen. Zusatze unterschiedlich strukturierter quartarer Ammoniumsalze als Leitsalz verandern das prozentuale Verhaltnis (C6H5)3P/(C6H5)2PCH3 nicht, wohl aber der Zusatz von Essigsaure, welche die Bildung von Methyl(diphenyl)phosphin begunstigt. - Bei den Cycloalkyl(triphenyl)phosphoniumsalzen mit Cyclohe…
Dienediolates of unsaturated carboxylic acids in synthesis. Aldehydes and ketones from alkyl halides, by ozonolysis of β,γ-unsaturated α-alkyl carbox…
1997
Abstract A convenient two-step procedure for a two carbon homologative conversion of alkyl halides into aldehydes and methyl ketones by α-alkylation of unsaturated carboxylic acids, followed by ozonolysis is developed and applied to the synthesis of ω-chloro aldehydes. Triethylamine is superior to dimethyl sulfide or triphenylphosphine for cleavage of the ozonides, except when aldol condensation side reactions require use of protic solvents and iodide salts. Cleavage of the ozonides by triethylamine is shown to occur mainly through a reductive process.
C—br insertion reactions in rhodium and iridium compounds containing an ortho-halo-arylphosphine. X-ray structures of two ortho-metallated compounds …
1988
Abstract A comparative study of the reaction of rh and ir complexes with the ortho-bromo-arylphosphine PCBr [PCBr = P(o-BrC6F4)(C6H5)2], is presented. Various PCBr complexes of Ir(I) and Rh(I) undergo rapid insertion of the metal atom into a CBr bond provided the phosphine is coordinated in a η2-mode (Pbr). If the Br coordination is substituted by a superior ligand such as CO or an olefin, no reaction occurs under normal conditions. PCBr complexes of the tervalent metals require a two-electron reduction step prior to the ortho-metallation reaction. Most intermediates were characterized by chemical and spectroscopic analysis. Two intermediates of general formula IrX2(η2-PC)(η-PCBr), [PC = …
Vergleichende dimerisierung der enantiomere von Oct-1-in-3-ol mit chiralen rhodium-phosphan-komplexen
1996
Abstract Three optically active phosphanes ([(S)-2-methylbutyl]3−nP[phenyl]n(n = 0, 1, 2), were tested as ligands in rhodium(I) complexes to form catalysts for the enantioselective dimerisation of (R)- and (S)-oct-1-yn-3-ol. The catalytic reaction provides enantioselectivity for this type of CC bond formation. For reactions at 45–75°C and depending on the P-ligand used the rates vary for both enantiomers from 6:1 to 50:1 in favour of the (S)-octynol.
Inhibitoren der Korrosion 10 (1). Nachweis der Sekundärinhibition durch Allyl-triphenyl-phosphonium- bzw. arsoniumbromid und N-Allyl-chinaldiniumbrom…
1971
Triphenyl-allyl-phosphonium- (1) und -arsoniumsalze (2) sowie Allyl-chinaldinium-bromid (4) sind Korrosionsinhibitoren mittlerer Wirksamkeit. Sie werden von Carbonyleisenpulver im sauren Medium zu Triphenylphosphin bzw. Triphenylarsin bzw. Chinaldin reduziert. Triphenylphosphin und Triphenylarsin, die sich als Schicht auf dem Carbonyleisenpulver befinden, konnen nach Extraktion dunnschichtchromatographisch identifiziert werden. Die Allylgruppe wird aus den Verbindungen 1, 2 und 4 durch Eisen als Propen, Propan und wahrscheinlich als Cyclopropan abgelost. Die gaschromatographisch bestimmten Mengen an Kohlenwasserstoffen stehen in guter Ubereinstim-mung mit den gravimetrisch ermittelten Werte…
Complexation of phosphine ligands with peracetylated β-cyclodextrin in supercritical carbon dioxide: spectroscopic determination of equilibrium const…
2007
The interaction between peracetylated beta-cyclodextrin and several triphenyl phosphine derivatives was studied in supercritical carbon dioxide (scCO2) by UV-visible spectroscopy. The equilibrium constant for a 1:1 complexation reaction was obtained from titration spectra and calculated using two established mathematical models. The values of the equilibrium constants are 1-3 orders of magnitude smaller than those obtained in aqueous solution with analogous phosphines. This is likely due to the absence in scCO2 of the hydrophobic effect, which is replaced by a corresponding, but weaker, CO2-phobic effect. The largest value of Kf was found for complexes of diphenyl(4-adamantylphenyl)phosphin…
Stereoselective synthesis of unsaturated and functionalized L-NHBoc amino acids, using Wittig reaction under mild phase-transfer conditions.
2012
The stereoselective synthesis of a new amino acid phosphonium salt was described by quaternization of melting triphenylphosphine with the γ-iodo NHBoc-amino ester, derived from L-aspartic acid. The deprotection of the carboxylic acid function to afford the phosphonium salt with a free carboxylic acid group was achieved by a palladium-catalyzed desallylation reaction. This phosphonium salt was used in the Wittig reaction with aromatic or aliphatic aldehydes and trifluoroacetophenone, under solid-liquid phase-transfer conditions in chlorobenzene and in the presence of K(3)PO(4) as weak base, to afford the corresponding unsaturated amino acids without racemization. Thus, the reaction with subs…
ChemInform Abstract: Applications and Stereoselective Syntheses of P-Chirogenic Phosphorus Compounds
2016
Phosphorus compounds bearing chirality on the P-center are usually qualified as P-chirogenic or P-stereogenic. This chemical class concerns natural products, agrochemistry, molecular materials, biology and pharmacy, although it is certainly in coordination chemistry and in asymmetric catalysis using chiral transition metal complexes that P-chirogenic phosphorus compounds are the most used. The chiral phosphine ligands and their uses in asymmetric metal-catalyzed reactions have been widely reviewed in literature. However, an overview covering the applications as well as the stereoselective syntheses of all classes of phosphorus compounds has not yet been provided. This review reports the bes…
Über makrozwitterionen, 9. Über den mechanismus der anionischen polymerisation von acrylnitril mit tertiären phosphinen unter Zusatz von LiCl
1974
Die anionische Polymerisation von Acrylnitril mit tertiaren Phosphinen in Dimethylformamid bei 25°C wurde unter Zusatz von LiCl untersucht. Es zeigte sich, das durch den Salzzusatz mit Triphenylphosphin als Initiator eine Polymerisation uber Makrozwitterionen ermoglicht wird und mit Triathylphosphin die (auch ohne Salzzusatz schon mogliche) Makrozwitterionenbildung starker auftritt. The effect of LiCl on the polymerization of acrylonitrile initiated by tertiary phosphines at 25 C in dimethylformamide was studied. Macrozwitterions are formed only in the presence of the added salt when triphenylphosphine is used as an initiator. In the system initiated by triethylphosphine formation of macroz…