Extracurricular laboratory:new discovery of 1,2-Bis(diphenylphosphino)benzene

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A catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes, but it must appear in at least one of the elementary reactions in the mechanism for the catalyzed reaction. 13991-08-7, Name is 1,2-Bis(diphenylphosphino)benzene, molecular formula is C30H24P2. In a Article,once mentioned of 13991-08-7, Product Details of 13991-08-7

Heterobifunctional phosphorus compounds have been prepared by oxidizing one phosphorus atom of a bis(phosphine) with azides.A variety of backbone structures have been used with one and two carbon chains, saturated and unsaturated structures and RN.Some degree of steric control appears to limit the extent of oxidation in cis bis(phosphines) with rigid backbones.Trimethylsilyl azide gives silylated iminophosphoranes with a reactive functionality on the imine nitrogen which can be replaced via metathetical elimination of Me3SiX or converted to the trimethylsilyloxy metal derivative by rearrangement of the trimethylsilyl group to terminal oxygen of a highly oxidized metal oxo precursor.Structural features of several examples of the heterobifunctional phosphorus compounds and their derivatives are described.

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Reference:
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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(Chemical Equation Presented) A highly efficient Mukaiyama aldol reaction between ketones and trimethylsilyl enolates catalyzed by sodium phenoxide-phosphine oxides as simple homogeneous Lewis base catalysts (0.5-10 mol %) was developed, which minimized competing retro-aidol reaction. For a variety of aromatic ketones and aldimines, aldol and Mannich-type products with an alpha-quaternary carbon center were obtained in good to excellent yields. Up to 100 mmol scale of benzophenone and trimethylsilyl enolate with 0.5 mol % of catalyst was established in 97% yield (34.8 g).

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Reference:
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 catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes, but it must appear in at least one of the elementary reactions in the mechanism for the catalyzed reaction. 13991-08-7, Name is 1,2-Bis(diphenylphosphino)benzene, molecular formula is C30H24P2. In a Article,once mentioned of 13991-08-7, Application In Synthesis of 1,2-Bis(diphenylphosphino)benzene

Reaction of silver(I) bromide with equimolar amounts of the rigid diphos ligands 1,2-bis(diphenylphosphano)benzene (dppbz) and 4,5-bis(diphenylphosphano)-9,9-dimethyl-xanthene (xantphos) in acetone and acetonitrile led to the corresponding chelates [Ag(mu2-Br)(dppbz)]2 (1) and [AgBr(xantphos)] (2). Treatment of 1 and 2 with pyridine-2-thione (py2SH) in ethanol gave the mixed-ligand complexes [AgBr(dppbz)(py2SH)] (3) and [AgBr(xantphos)(py2SH)] (4), respectively. Compounds 1, 2 and 4 have been characterized by X-ray diffraction, establishing distorted tetrahedral or trigonal planar coordination geometries of the silver atoms.

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Reference:
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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Five iridium complexes containing bidentate phosphine ligands, IrH(CO)(PPh3)(BPPB) [BPPB = 1,2-bis(diphenylphosphino)benzene] (1), IrH(CO)(PPh3)(BISBI) [BISBI = 2,2?-bis(diphenylphosphinomethyl)-1,1?-biphenyl] (2), IrH(CO) (PPh3)(BDNA) [BDNA = 1,8- bis(diphenylphosphinomethyl)naphthalene] (3), IrH(CO)(PPh3)(BDPX) [BDPX = 1,2-bis(diphenylphosphinomethyl)benzene] (4), and IrHCI(CO)(PCP) [PCP-H = 1,3-bis(diphenylphosphinomethyl)benzene] (5) were synthesized. Their compositions and structures were identified by elemental analysis, FTIR, 31P{(1H}) NMR and 1H NMR. The molecular structure of IrH(CO)(PPh3)(BDNA) determined by single crystal X-ray diffraction indicated a trigonal bipyramidal structure with the three phosphorus atoms in the equatorial plane. The crystal belonged to triclinic system, P1 space group, a = 11.47 A, b = 11,65 A, c = 19.20 A, alpha = 81.95, beta = 75.60, gamma = 70.60, and Z = 2. The catalytic hydrogenation activities and selectivities of the five complexes as catalysts for citral and cinnamaldehyde were investigated. Complexes 1-4 showed high selectivity for the hydrogenation of C=O group in citral. High selectivity for the hydrogenation of C=O group in cinnamaldehyde catalyzed by complex 4 could be obtained in the presence of excess amount of ligand (BDPX).

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Reference:
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

Discovery of 1,2-Bis(diphenylphosphino)benzene

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A great deal of research effort has been put in green energy applications in the past few decades based on organic optoelectronics. Compared with conventional inorganic semiconductors, organic counterparts offer a much simpler strategy for low-cost mass production and structural modification. Hence, continuous and intensive academic and industrial research works have been done in these areas. In terms of the materials used, transition-metal complexes with the unique features of the transition metal centers represent a large group of candidates, showing high performance in energy conversion technologies. However, the commonly used transition metals, like Pt(II), Ir(III) and Ru(II), are expensive and of relatively low abundance. Concerning elemental sustainability and marketability, some abundant and cheaper metals should be investigated and further developed to replace these precious metals. Cu(I) complexes have shown their potentiality in solar energy harvesting and light emitting applications, due to their well-studied photophysics and structural diversity. In addition, copper is one of the earth-abundant metals with less toxicity, which makes it competitive to precious transition metals. As a result, a series of rational molecular engineering has been developed to boost the device performance of copper complexes. In this review, the recent progress of copper complexes in the fields of organic light emitting devices (OLEDs), photovoltaic cells (dye-sensitized solar cells (DSSCs) and bulk heterojunction solar cells (BHJSCs)) in the past two decades will be presented. Representative examples are chosen for discussion.

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Reference:
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 reactions of (Me2S)BH2Br and (Me2S)BHBr2 with equimolar quantities of l,2-bis(diphenylphosphanyl)ethene (1) or -benzene (2) lead to cyclic, cationic bis(phosphane)boranes {4: [(1)BH2]+ [(1)BH2]; 5: [(l)BHBr]+ [(1)BH2]; 6: [(2)BH2]+ Br-; 7: [(2)BHBr]+ The (1)BH2]+ counterions can be exchanged in metathesis reactions (e.g. with AgBF4 to afford 4a). The tritertiary phosphane bis[2-(diphenylphosphanyl)phenyl]phenylphosphane (3), reacts with (Me2S)BHBr2 to give bicyclic dicationic tris(phosphane)borane 8, [(3)BH]2+-2 Br-, which can be converted into the bis(hexafluorophosphate) 8a using NH4PF6. All compounds have been characterized by analytical and NMR-spectroscopic data. The crystal and molecular structures of 5-7 have been determined by single-crystal Xray diffraction.The five-membered rings C2P2B have an envelope conformation and show no sign of electron delocalization. Attempts to deprotonate the B-H functions in 5-8 have not been successful. Clearly, the two (5-7) or three phosphonium centers (8) adjacent to the boron atom are not sufficient to induce an “umpolung” of the B-H group. WILEY-VCH Verlag GmbH,.

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Reference:
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 to complex silver complex double-emitting dye, synthetic method and its application, the invention relates to a process to complex silver complex double-emitting dye, synthetic method and its application. The present invention is how to solve the existed before the phosphorescent and the thermal excitation delay fluorescent dye exciton accumulated as a result of the quenching effect, to cause the device to performance and stability is poor, the dye in order to process to ligand and AgX coordination form, method is as follows: the 1mmol process to ligand, 0.5 – 1mmol of AgX, 5 – 10 ml of DCM mixed, 40 C reaction 10 – 36 hours later, turns on lathe does, DCM and PE for the eluent to the column chromatography purification, get the process to complex silver complex. The material which has the characteristics of emission, reduced to the maximum limit of excitons accumulated, improve the device efficiency, the efficiency of the suppression device of the roll-off. To achieve the maximum utilization of the electroluminescent in the process. (by machine translation)

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Reference:
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 bidentate phosphine ligands 1,2-bis(diphenylphosphino)ethane (dppe), 1,2-bis(diphenylphosphino)ethene (dppee) or 1,2-bis(diphenylphosphino)benzene (dppbe) undergo reactions with the rhenium(V)-imido complex, trans-Re(NPh)Cl3(PPh3)2, in refluxing alcoholic solvent to give mixtures of fac-Re(NPh)Cl3(L-L) and trans-[Re(NPh)X(L-L)2]2+. Mild reaction conditions favor the monosubstituted complexes and harsh conditions favor the salts. The electrochemical properties of the salts reveal subtle differences associated with the backbone of the ligands. The structure of the hydroxy-imido salt trans-[Re(NPh) (OH) (dppbe)2] (ClO4)2?2H2O was determined and shows the rhenium atom displaced 0.536(2) A above the P4 equatorial plane, the largest displacement observed for rhenium(V) compounds containing pi-donor ligands, and the Re-N(imido) distance of 1.757(10) A is the longest observed for rhenium(V)-imido compounds.

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Reference:
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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Correlation between the photophysics and the structures of three Ag(I)-bis(diphosphine) complexes ([Ag(dppbz)2]NO3 (2 · NO3), [Ag(dppe)2]NO3 (3·NO 3), and [Ag(dppp)2]NO3 (3·NO 3) (dppbz = 1,2-bis(diphenylphosphino)benzene, dppe = 1,2-bis(diphenylphosphino)ethane, dppp = 1,3-bis(diphenylphosphino)propane) has been investigated using temperature-dependent emission measurements and electrochemical and theoretical methods. All three Ag(I)-bis(diphosphine) complexes have relatively low oxidation potential, which allows metalto-ligand charge transfer (MLCT) contribution in the lowest excited state of the tetrahedral geometry, which is difficult in other Ag(I) complexes. Both 1 · NO3 and 2 · NO3 show orange phosphorescence with moderate quantum yield in airfree methanol at room temperature, while 3 · NO3 is less emissive in solution at room temperature. In all three complexes the temperature-dependent luminescence measurements in EtOH/MeOH 4:1 (v/v) solution indicate the blue-shift of the emission maximum and the increase of the emission intensity on lowering the temperature. In particular, the sequential emission spectral change with decreasing temperature is observed in 1 · NO3 and 2 · NO3. In the glass state at 90 K, all three complexes show intense blue phosphorescence. The theoretical calculation using density functional theory (DFT) suggests that the orange and blue emissions mainly originate from the 3MC excited state based on a square-planar geometry and the 3IL+3MLCT excited state based on a tetrahedral geometry, respectively.

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Reference:
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 use of iron-catalysed organic transformations in the total syntheses of natural products has increased significantly. Iron-catalysed cross-coupling reactions are now widely applied in total syntheses and many other transformations, such as alkene functionalisation, oxidation, and cyclisation. The development of these processes, as well as many examples of their use in target synthesis, is presented here. 1 Introduction 2 Cross-Coupling Reactions 3 Functionalisation of Unactivated Alkenes 4 Carbocyclisation Reactions 5 Oxidations 6 Further Examples 7 Conclusions.

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Reference:
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