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Cluster growth reactions with selenido-carbonyl clusters – Synthesis, characterisation and theoretical study of the dimetallic closo clusters [WRu3(mu4-Se2(mu-CO)4(CO)6(L)2] (L = Phosphane) and of the donor-acceptor adduct [(CO)5W(mu4-Se)Ru3(mu3-Se)(CO)7{P(CH2Ph)Ph2}2]

The open-triangular, nido clusters of the type [Ru3(mu 3-Se)2-(CO)7(L)2] [L = PPh 3, PPh2(OMe), PPh2(Me), P(p-MeO-C 6H4)3] react at room temperature with [W(CO)3(MeCN)3] to give the dimetallic closo clusters [WRu3(mu4-Se)2(mu-CO)4-(CO) 6(L)2]. When L is P(CH2Ph)Ph2 the donor-acceptor adduct [(CO)5W(mu4-Se)Ru 3(mu3-Se)(CO)7(P(CH2Ph)Ph 2)2] is obtained where the nido cluster [Ru 3(mu3-Se)2(CO)7(L)2] interacts with the fragment W(CO)5 through a selenido ligand. DFT calculations, performed on the model species [WRu3(mu4- Se)2(mu-CO)4(CO)6(PH3) 2] and [(CO)5W(mu4-Se)Ru3(M 3-Se)-(CO)7(PH3)2], showed that the computed total energy of the latter is 1.1 eV lower than that of the former. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Olefination reactions through phosphazenes

The first synthesis of di-, tri- and tetrasubstituted alkenes through reaction of lithium P-diphenyl(alkyl)(N-carboxymethyl)phosphazenes with aldehydes and ketones is reported.

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Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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ELECTROCHEMICAL SYNTHESIS OF TERTIARY PHOSPHINES FROM ORGANIC HALIDES AND CHLOROPHOSPHINES

The electrochemical synthesis of a wide range of tertiary mono- and diphosphines has been achieved in very simple and mild conditions, in an undivided electrolytic cell with a sacrificial anode of magnesium.

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Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Synthesis, Characterization, DNA Interaction Study, Antibacterial and Anticancer Activities of New Palladium(II) Phosphine Complexes

A series of palladium(II) complexes with N,N-dimethylthiourea and phosphines [tri-p-tolylphosphine (Tptp), benzyl(diphenyl)phosphine (Bdp), cyclohexyl(diphenyl)phosphine (Cdp)] were synthesized by the direct reaction of K2[(PdCl4)] with the corresponding phosphines and then with N,N-dimethylthiourea at a molar ratio of 1: 2: 2. The general formula of these complexes is [Pd(L1)2(L2)2]Cl2, where L1 = N,N-dimethylthiourea (Dmtu), L2 = Tptp, Bdp, Cdp. The complexes were characterized by elemental analyses, multinuclear NMR (1H, 13C, 31P), and FT-IR. The complex with cyclohexyl(diphenyl)phosphine was also characterized by single crystal X-ray analysis. The spectral and crystallographic data suggest monodentate coordination of dimethylthiourea through the sulfur atom and of the phosphine ligand through the phosphorus atom and distorted square planar environment of palladium(II). The synthesized complexes have been screened for DNAbinding, antibacterial, cytotoxic, and antitumor activities. The complexes show interaction with DNA via intercalative mode. The complexes show good activity against both gram positive and gram negative bacteria as compared to that of a standard drug, Imipenem. Their antitumor activity against MCF7 tumor cell line was found to be comparable with doxorubicin. MTT assay was used to investigate the cytotoxicity of the studied compounds having activity order: 3 > 2 > 1.

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Process for preparing a branched olefin, a method of using the branched olefin for making a surfactant, and a surfactant

A process for preparing branched olefins comprising 0.5% or less quaternary aliphatic carbon atoms, which process comprises dehydrogenating an isoparaffinic composition over a suitable catalyst which isoparaffinic composition comprises paraffins having a carbon number in the range of from 7 to 35, of which paraffins at least a portion of the molecules is branched, the average number of branches per paraffin molecule being at least 0.7 and the branching comprising methyl and optionally ethyl branches, and which isoparaffinic composition may be obtained by hydrocracking and hydroisomerization of a paraffinic wax; a method of using olefins for making an anionic surfactant, a nonionic surfactant or a cationic surfactant, in particular a surfactant sulfate or sulfonate, comprising converting the branched olefins into the surfactant; and an anionic surfactant, a nonionic surfactant or a cationic surfactant which is obtainable by the method of use.

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Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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ORGANOARSENEVERBINDUNGEN: 39 SUBSTITUERTE BENZYLPHOSPHINE UND -ARSINE ALS LEICHT ZUGAENGLICHE BIDENTATE LIGANDEN

2-Hydroxybenzylamines or 2- and 4-aminobenzylamines react with diphenylphosphine at higher temperature to give hydroxy-substituted and aminosubstituted benzylphosphines, respectively.This reaction fails in the case of alkoxy or dialkylaminobenzyl amines.The corresponding benzylphosphines have been obtained after conversion of the benzylamines into the quaternary ammonium salts and susequent addition of sodium phosphide. 2-Alkylmercaptobenzylphosphines have been synthesized in a similar manner.An elimination-addition-mechanism or a substitution mechanism have been proposed due to the different reaction conditions required.The nitrogen- or oxygen-substituted benzylarsines have been prepared by both reaction paths. 3-Dimethylaminomethyl indole reacts with secondary phosphines or arsines in accordance with the proposed mechanism to give indolylmethyl phosphines and arsines, respectively.

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Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Orthopalladated phosphinite complexes as high-activity catalysts for the suzuki reaction

The synthesis of a range of phosphinite ligands PR2(OAr) (R = Ph, iPr), their simple complexes with palladium(II) and their palladacyclic complexes has been investigated. The crystal structure of one of the palladacyclic complexes, [{Pd(mu2-Cl)} {kappa2-P, C-PiPr2(OC6H2-2,4-t Bu2)} 2], has been determined. The palladacyclic complexes show extremely high activity in the Suzuki coupling of aryl bromide substrates with phenylboronic acid and can also be used with alkylboronic acid substrates. A comparison of the phosphinite-based catalysts with equivalent phosphite- and phosphine-based systems highlights their superior activity. The orthometallation of the phosphinite ligand in the pre-catalyst appears to be crucial for optimal activity. While the phosphinite palladacycles are only moderately active in the coupling of activated and non-activated aryl chloride substrates, their tricyclohexylphosphine adducts prove to be highly active in the coupling of the deactivated substrate, 4-chloroanisole. This high activity compared with other palladacyclic systems is explained in terms of catalyst longevity. The orthometallated precatalysts appear to undergo a reductive activation process to generate zerovalent active catalysts via reductive elimination of the orthometallated ring with a phenyl introduced by the boronic acid. This implies that the true active catalysts contain 2-arylated ligands. Catalysts formed with such 2-arylated ligands tend to show markedly higher activity than their parent ligands.

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Anticancer metallopharmaceutical agents based on mixed-ligand palladium(II) complexes with dithiocarbamates and tertiary organophosphine ligands

Mixed-ligand palladium(II) complexes of the type [(DT)Pd(PR 3)Cl], where DT = diethyldithiocarbamate (1), dibutyldithiocarbamate (2,3), dipropyldithiocarbamate (4,5), bis(2-methoxyethyl)dithiocarbamate; PR3 = benzyldiphenylphosphine (1,4), diphenyl-o-tolylphosphine (2), diphenyl-t-butylphosphine (3), P-chlorodiphenylphosphine (5) and triphenylphosphine (6), have been synthesized and characterized by elemental analyses and FT-IR, Raman and multinuclear NMR spectroscopy. The structures of compounds 1 and 2 were determined by single-crystal X-ray diffraction (XRD) measurements and these analyses showed that the complexes have pseudo square-planar geometry around the Pd(II) and that the dithiocarbamate ligand is bound in a bidentate fashion, while the remaining two positions are occupied by a tertiary organophosphine and a chloride ligand. The anticancer studies showed that the Pd(II) complexes are highly active against cisplatin-resistant DU145 human prostate carcinoma (HTB-81) cells with the highest activity shown by compound 6 (IC50 = 2.12 mum). The redox behavior and ds-DNA-denaturing ability of the complexes were studied by cyclic voltammetry and two reduction and one oxidation waves were observed. The decrease in the reduction peak currents illustrated the consumption of the mixed-ligand drug by the DNA molecule. Copyright

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Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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SYNTHESIS OF SOME FUNCTIONALIZED PHOSPHINOCARBOXYLIC ACIDS

Various functionalized phosphinocarboxylic acids have been prepared by a number of complementary methods.Reactions of relatively electron-poor secondary phosphides with electron-rich halocarboxylates in liquid ammonia give high yields of phosphinocarboxylates.The substitution reactionmay proceed by a classical SN2 mechanism or by an SN rad mechanism.Reduction of the carboxilate can be a deleterious side reaction in the preparation of phosphinoacetic acids.Several phosphinopropionic acids are prepared by the Michael adition of diphenylphosphine to unsaturated esters.A valuable method proved to be the reaction of dichlorophosphinoacetic ester with functionalized organometallic reagents. Key words: Phosphine; carboxylic acid; ligand; functionalized; synthesis; NMR data.

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.7650-91-1, Name is Benzyldiphenylphosphine, molecular formula is C19H17P. In a Article£¬once mentioned of 7650-91-1, Application In Synthesis of Benzyldiphenylphosphine

Phosphine-directed C-H borylation reactions: Facile and selective access to ambiphilic phosphine boronate esters

Ambiphilic ligands have received considerable attention over the last two decades due to their unique reactivity as organocatalysts and ligands. The iridium-catalyzed C-H borylation of phosphines is described in which the phosphine is used as a directing group to provide selective formation of arylboronate esters with unique scaffolds of ambiphilic compounds. A variety of aryl and benzylic phosphines were subjected to the reaction conditions, selectively providing stable, isolable boronate esters upon protection of the phosphine as the borane complex. After purification, the phosphine-substituted boronate esters could be deprotected and isolated in pure form.

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate