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Effect of the Bite Angle of Diphosphine Ligands on Activity and Selectivity in the Nickel-catalysed Hydrocyanation of Styrene

The application of diphosphines with large bite angles (betan = 101-109 deg) in nickel catalysts leads to successful, regioselective hydrocyanation of styrene.

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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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A New Highly Efficient Amine-Free and Peroxide-Free Redox System for Free Radical Polymerization under Air with Possible Light Activation

Efficient redox initiating systems for radical polymerizations under air usually show some severe drawbacks such as handling and toxicity of the oxidizing agent (peroxides, persulfates, peroxidiphosphates, disulfides, etc.), toxicity of the reducing agent (aromatic amines such as 4-N,N-trimethylaniline), and more generally a low top surface conversion due to high oxygen inhibition. The originality of the proposed paper relies on the development of new redox initiating systems for the polymerization of (meth)acrylate monomers that does not contain any hazardous compound (no peroxide) and is amine-free (low toxicology issues). And these new systems that possess the advantages of redox-initiated polymerization (possibility to cure thick samples) can also be photoactivated in order to have a faster and better curing of the surface of the sample (advantages of the photopolymerization to overcome the oxygen inhibition). The light activations presented in this work have been done with light-emitting diodes (LEDs) as they have a low energy consumption and are safer to the user than UV light. Two wavelengths have been used: 405 nm (in the blue range of the spectrum) and 780 nm (in the near-infrared) showing the versatility of these new photo/redox initiating systems. In particular, the reactivity in the near-IR (not related to any heating of the sample) is a very original result. In addition with the presentation of the performance of the new systems in polymerization and photoactivated polymerization, a full analysis of the chemical mechanisms and species involved has been performed. Remarkably, the new proposed Cu(acac)2/2dppba system is also able to overcome the oxygen inhibition for free radical redox (photo)polymerization.

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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.161265-03-8, Name is (9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine), molecular formula is C39H32OP2. In a Article£¬once mentioned of 161265-03-8, SDS of cas: 161265-03-8

The coordination behaviour of large natural bite angle diphosphine ligands towards methyl and 4-cyanophenylpalladium(II) complexes

The structures of neutral and ionic 4-cyanophenylpalladium(II) and methylpalladium(II) complexes containing bidentate phosphine ligands were investigated in solution and in the solid state. Diphosphine ligands with a xanthene and a ferrocene backbone were used. New bis(dialkylphosphino) substituted Xantphos ligands were synthesised. 1H NMR and 31P NMR spectroscopy, conductivity measurements, UV-Vis spectroscopy, and X-ray crystallography were used to elucidate the structures of the complexes. Subtle changes of the phosphine ligands govern the coordination mode of the ligand. A variety of bidentate cis-, and trans-coordination and terdentate P-O-P, P-S-P and P-Fe-P coordination modes of the ligands were observed.

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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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New, Highly Efficient Work-Up Protocol for Sulfonated Diphosphines

Isolation of a series of sulfonated diphosphines via a new highly efficient method is described. The work-up procedure involves the precipitation of the sulfonated ligand prior to neutralization, and subsequent removal of the sulfuric acid by filtration and washing. Great advantages of this procedure are its simplicity and easiness to scale-up while co-production of large amounts of sulfate salts is avoided.

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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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Controllable Isomerization of Alkenes by Dual Visible-Light-Cobalt Catalysis

We report herein that thermodynamic and kinetic isomerization of alkenes can be accomplished by the combination of visible light with Co catalysis. Utilizing Xantphos as the ligand, the most stable isomers are obtained, while isomerizing terminal alkenes over one position can be selectively controlled by using DPEphos as the ligand. The presence of the donor?acceptor dye 4CzIPN accelerates the reaction further. Transformation of exocyclic alkenes into the corresponding endocyclic products could be efficiently realized by using 4CzIPN and Co(acac)2 in the absence of any additional ligands. Spectroscopic and spectroelectrochemical investigations indicate CoI being involved in the generation of a Co hydride, which subsequently adds to alkenes initiating the isomerization.

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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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OsXCl(phosphine)2(diamine) and OsXCl(diphosphine)(diamine) (X = Cl, H) Complexes for Ketone Hydrogenation

The osmium complex trans-[OsCl2(PPh3)2(en)] (2) was prepared by reaction of [OsCl2(PPh3)3] (1a) with ethylenediamine (en), whereas the diphosphine derivatives trans-[OsCl2(dppf)(NN)] (NN = en (3), bn (4; bn = 1,4-butanediamine)) and trans-[OsCl2(dpbp)(en)] (5) were obtained from 1a, dppf or dpbp, and the corresponding NN ligand in CH2Cl2 or toluene. An X-ray diffraction study has been provided for 3. The isolation of the chiral derivatives trans-[OsCl2(diphosphine)((R,R)-dpen)] (diphosphine = dppf (6), dpbp (7), (R,R)-skewphos (8)) was achieved by reacting 1a with the diphosphine and (R,R)-dpen in toluene. Treatment of the precursor [Os2Cl4(P(m-tolyl)3)5] (1b) with en afforded [OsCl2(P(m-tolyl)3)2(en)] (9), while reaction of 1b with dppb and N,N-dmen gave [OsCl2(dppb)(N,N-dmen)] (10). The chiral derivatives [OsCl2(diphosphine)(NN)] (11-21; diphosphine = (S)-MeObiphep, (R)-MeObiphep, (R)-xylMeObiphep, (R)-binap, (S)-xylbinap, (R)-xylbinap, (R,S)-Josiphos NN = en, (R,R)-dpen, (R)-daipen, (R,R)-dppn) were prepared from 1b and the corresponding diphosphine and NN ligands in toluene. The monohydride trans-[OsHCl(P(m-tolyl)3)2(en)] (22) was synthesized by reaction of 1b with H2 (1 atm) in the presence of NEt3, followed by addition of en in toluene. Similarly, trans-[OsHCl(dppf)(en)] (23) was synthesized from 1a, H2, and NEt3, followed by treatment with dppf and en. Complexes 2-5, 9, 10, 22, and 23 efficiently catalyzed the hydrogenation of acetophenone with H2 under low pressure (5 atm) at 60-70 C in ethanol (1-2 mol % of NaOEt) with the ratio S/C = 5000-10000. The chiral derivatives 6-8 and 11-21 afforded the asymmetric hydrogenation of acetophenone with up to 90% ee by combining bulky xylyl-substituted MeObiphep or binap-type ligands with (R)-daipen or (R,R)-dpen ligands. Catalytic transfer hydrogenation of acetophenone was observed with 3, 6, and 7 (S/C = 2000) in 2-propanol and in the presence of NaOiPr (2 mol %) at 60-82 C.

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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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An improved synthesis of 4-cyano-1,10-phenanthroline, 4,7-dicyano-1,10- phenanthroline and their bis(4,4?-di-tert-butyl-2,2?-bipyridine) ruthenium(II) complexes

This report describes a new palladium catalyzed synthesis of 4-cyano-1,10-phenanthroline (nphen, 1), 4,7-dicyano-1,10-phenanthroline (dnphen, 2) and their corresponding ruthenium complexes. The two cationic complexes, [(tbbpy)2Ru(nphen)]2+ 3 and [(tbbpy)2Ru(dnphen) ]2+ 4 (tbbpy = 4,4?-di-tert-butyl-2,2?-bipyridine), were synthesized using an improved microwave procedure. All compounds were fully characterized, including the solid-state molecular structures of the complexes. The influence of 1 and 2 on the metal-to-ligand charge transfer (MLCT) transitions were studied and compared to the ruthenium(II) polypyridyl complexes containing the related 4,4?-dicyano-2,2?-bipyridine (dnbpy) and the non-functionalized 1,10-phenanthroline (phen) ligand.

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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.161265-03-8, Name is (9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine), molecular formula is C39H32OP2. In a Patent£¬once mentioned of 161265-03-8, Product Details of 161265-03-8

NEW AZABENZIMIDAZOLE DERIVATIVES

The present invention relates to compounds of general formula I, wherein the group R1, R2, X and Y are defined as in claim 1, which have valuable pharmacological properties, in particular bind to the AMP-activated protein kinase (AMPK) and modulate its activity. The compounds are suitable for treatment and prevention of diseases which can be influenced by this receptor, such as metabolic diseases, in particular diabetes type 2.

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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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Sterically controlled reactivity of palladium(II) tetranuclear cyclometallated complexes. Crystal and molecular structure of the novel tetranuclear compound [Pd2{1,3-[C(H)=NCH2C4H7O] 2C6H2}-(mu-Cl)(Cl)(PPh3)] 2

The reaction of the Schiff base ligands 1,3-[C=N(H)CH2C4H7O]2C 6H4 (1) and 1,4-[C=N(H)CH2C4H7O]2C 6H4 (14) with palladium(II) acetate in toluene gave the acetato-bridged cyclometallated compounds [Pd2{1,3-[C(H)=NCH2C4H7O] 2C6H2}(mu-AcO)2]2 (2) and [(mu-AcO)Pd{1,4-[C(H)=NCH2C4H7O] 2C6H2}Pd(mu-AcO)]n (15). Reaction of 2 and 15 with aqueous sodium chloride gave the chloro-bridged cyclometallated compounds [Pd2{1,3-[C(H)=NCH2C4H7O] 2C6H2}(mu-Cl)2]2 (3) and [(mu-Cl)Pd{1,4-[C(H)=NCH2C4H7O] 2C6H2}Pd(mu-Cl)]n (16), respectively, after a metathesis reaction. Reaction of 3 with triphenylphosphine in a 1:2 molar ratio gave the tetranuclear complex [Pd2{1,3-[C(H)=NCH2C4H7O] 2C6H2}(mu-Cl)(Cl)(PPh3)] 2 (4), where only one of the bridging PdCl2Pd moieties was cleaved, and which was characterized by X-ray crystal structure analysis. However, reaction of 16 with PPh3 gave the dinuclear complex [(PPh3)(Cl)Pd{1,4-[C(H)=NCH2C4H 7O]2C6H2}Pd(PPh3)(Cl)] (17) after a full bridge-splitting reaction. Similarly, treatment of 3 with PMe2Ph, pyridine and thallium acetylacetonate produced the dinuclear complexes 5, 6 and 7, respectively. Treatment of 4 with pyridine in a 1:2 molar ratio, and with 4,4?-dipyridyl in an 1:1 molar ratio, gave the di- and tetranuclear complexes 12 and 13, respectively. Reaction of 3 with the tertiary diphosphine cis- Ph2PCH=CHPPh2 in a 1:2 molar ratio yielded the tetranuclear complex [Pd2{1,3- [C(H)=NCH2C4H7O]2C6H 2}(mu-Cl)(Ph2PCH=CHPPh2-P,P)][Cl] 2 (8) after selective splitting of one of the PdCl2Pd bridging moieties. However, reaction of 3 with cis-Ph2PCH=CHPPh2 and Ph2P(CH2)2PPh2 in 1:4 molar ratios gave the dinuclear complexes 9 and 10, respectively. Reaction of 3 with the diphosphine Ph2PC5H4FeC5H4PPh 2 in a 1:2 molar ratio yielded the trinuclear complex [Pd2{1,3- [C(H)=NCH2C4H7O]2C6H 2}(mu-Ph2PC5H4FeC5H 4PPh2)] (11), with the diphosphine bridging the two palladium atoms of the dicyclometallated moiety.

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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 BENZIMIDAZOLE COMPOUNDS

Provided are methods for the synthesis of heterocyclic compounds such as benzimidazole carboxylic acid core structures having Formula Ia-1 and their synthetic intermediates:wherein Z, X1 , X2 , X5 , R2 and R10 are as defined herein. Compounds of Formula Ia-1 and their synthetic intermediatescan be used to prepare heterocyclic derivatives such as benzimidazole derivatives

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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