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(Chemical Equation Presented) Here we report the electrocatalytic reduction of protons to hydrogen by a novel S2P2 coordinated nickel complex, [Ni(bdt)(dppf)] (bdt = 1,2-benzenedithiolate, dppf = 1,1?-bis(diphenylphosphino)ferrocene). The catalysis is fast and effi cient with a turnover frequency of 1240 s-1 and an overpotential of only 265 mV for half activity at low acid concentrations. Furthermore, catalysis is possible using a weak acid, and the complex is stable for at least 4 h in acidic solution. Calculations of the system carried out at the density functional level of theory (DFT) are consistent with a mechanism for catalysis in which both protonations take place at the nickel center.

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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 novel and convenient one-pot synthesis of ruthenium(II) dihydride phosphine complexes from the air-stable [RuCl2(COD)]x, the appropriate phosphine, and NaOH in sec-butyl alcohol under argon at 80 C is reported. A series of chelating (dcpm, dcpe, dppe, dppb, dppp, dppf, and depe) and monodentate phosphine (PEt3 and PPh3) complexes have been synthesized using this methodology. The crystalline products are isolated in high yield. These dihydride complexes have been shown to be useful precursors to cationic dihydrogen hydride complexes, some of which exhibit significant activity as hydrogenation catalysts.

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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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Fluorophores based on the 4-bora-3a,4a-diaza-s-indacene (aka boron dipyrromethene, boron dipyrrin, or BODIPY) platform have found diverse applications in different fields of modern science, medicine and (bio)technology. In this review we describe the numerous postfunctionalization methodologies of the boron dipyrromethene core designed and realized by research groups around the globe. In the postfunctionalization approach, boron dipyrromethenes with reactive functionalities attached directly to the core (halogen or hydrogen atoms, methyl, formyl, or alkylthio groups) are used as starting materials for further derivatization. The various synthetic methods towards these starting compounds and their postmodification are reviewed. We discuss the different strategies devised for postderivatization of the BODIPY nucleus at all possible positions (the pyrrole carbons, the meso-carbon, and the boron atom) and compare them concisely with the standard prefunctionalization methodology. Important properties and applications of a number of substituted BODIPYs made by the methods described in this review are also presented.

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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 reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.166330-10-5, Name is (Oxybis(2,1-phenylene))bis(diphenylphosphine), molecular formula is C36H28OP2. In a Article,once mentioned of 166330-10-5, Quality Control of: (Oxybis(2,1-phenylene))bis(diphenylphosphine)

Herein we describe an efficient protocol for the regioselective addition of 1,3-dicarbonyl compounds to internal alkynes catalyzed by rhodium/Lewis acid catalysts. The corresponding branched/linear allylic alkylation products could be selectively obtained in good yields. Rh-H species were considered to be generated by direct C-H oxidative addition of 1,3-dicarbonyl compounds with rhodium catalyst with the assistance of Lewis acid. Moreover, a retro-allylic alkylation process was observed in this transformation.

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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 present invention relates to substituted imidazopyrazine compounds of general formula (I), in which R1, R2, R3, R4 and R5 are as defined in the claims, to methods of and intermediates for preparing said compounds, to pharmaceutical compositions and combinations comprising said compounds and to the use of said compounds for manufacturing a pharmaceutical composition for the treatment or prophylaxis of a disease, in particular of a hyper-proliferative and/or angiogenesis disorder, as a sole agent or in combination with other active ingredients.

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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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Methoxycarbonylation provides a one-step synthesis to valuable ester products utilised in both the fine and heavy chemical industry. However, in general, reaction rates for longer chain alkenes are poor which renders industrial implementation economical unviable. In cases where suitable rates are achieved, the requisite reagents are costly and in addition, the catalyst complexes readily decompose at elevated temperatures. This paper describes the use of an alternative ligand structural motif for the efficient methoxycarbonylation of terminal and internal medium chain alkenes to their corresponding esters. Promising results were obtained using a catalyst complex generated in situ from an unsymmetrical diphosphine ligand based on a ferrocene backbone, Pd(OAc)2 and methane sulfonic acid.

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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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Heteroleptic copper(I) complexes have been prepared from a macrocyclic ligand incorporating a 2,9-diphenyl-1,10-phenanthroline subunit (M30) and two bis-phosphines, namely bis[(2-diphenylphosphino)phenyl] ether (POP) and 1,3-bis(diphenylphosphino)propane (dppp). In both cases, the diphenylphosphino moieties of the PP ligand are too bulky to pass through the 30-membered ring of M30 during the coordination process, hence the formation of C2v-symmetrical pseudo-rotaxanes is prevented. When POP is used, X-ray crystal structure analysis shows the formation of a highly distorted [Cu(M30)(POP)]+ complex in which the POP ligand is only partially threaded through the M30 unit. This compound is poorly stable as the CuI cation is not in a favorable coordination environment due to steric constraints. By contrast, in the case of dppp, the bis-phosphine ligand undergoes both steric and topological constraints and adopts a nonchelating coordination mode to generate [Cu2(M30)2(mu-dppp)](BF4)2. This compound exhibits metal-to-ligand charge transfer (MLCT) emission characterized by a very large Stokes’ shift (?200 nm) that is not attributed to a dramatic structural distortion between the ground and the emitting states but to very weak MLCT absorption transitions at longer wavelengths. Accordingly, [Cu2(M30)2(mu-dppp)](BF4)2 shows unusually high luminescence quantum yields for CuI complexes, both in solution and in the solid state (0.5 and 7%, 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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A new series of luminescent mononuclear CuI complexes with functionalized 6-cyano-2,2?-bipyridine chelating ligands, [Cu(xantphos)(cbpy)]ClO4 (1), [Cu(xantphos)(4,4′-Me2cbpy)]ClO4·CH2Cl2·H2O (2), and [Cu(POP)(cbpy)]ClO4·CH2Cl2 (3) (xantphos = 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; POP = bis(2-diphenylphosphinophenyl)ether; 4,4′-Me2cbpy = 4,4′-dimethyl-6-cyano-2,2?-bipyridine; cbpy = 6-cyano-2,2?-bipyridine) have been successfully prepared, and their structures and photophysical properties are investigated. Single crystal structures of the three complexes reveal a distorted tetrahedral coordination geometry around the CuI centres with the P atoms of diphosphane ligands and N donors of 2,2?-bipyridine ring. Luminescence measurements indicate that these CuI complexes display good emission properties both in the solution and solid states at room temperature, which can be well modulated through modifying the structure of 6-cyano-2,2?-bipyridine. It is shown that the introduction of two electron-donating methyl groups at the 4,4′-positions of the 6-cyano-2,2?-bipyridine is favourable to enhance the luminescence properties of the CuI complexes.

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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

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

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The complexation of the mixed bidentate ligands 1-diphenylphosphino-1?-diphenylthiophosphinoferrocenyl and 1,2-bis-(diphenylphosphino)ferrocenyl with rhodium(I) and palladium(II) species yield a range of mono- and dirhodium or palladium complexes. Their interest as possible catalysts for alkene hydroformylation and alkoxycarbonylation and Heck coupling reactions has been assessed. Fe[C5Me4P(S)Ph2][C5Me 4PPh2]PdCl2 and Fe[C5H2-1,2-(PPh2)2-4- tBu][C5H5]PdCl2 have been characterized by single-crystal X-ray diffraction studies.

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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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Nitroalkanes undergo decarboxylative allylation in the presence of vinyl-substituted cyclic carbonates, providing a wide variety of functionalized homoallylated compounds with exquisite stereocontrol. This Pd-mediated procedure features operational simplicity, versatile substrate combinations, and also allows for the sequential introduction of different allyl groups in the nitroalkane scaffolds with high levels of stereocontrol through the intermediacy of a (Z)-configured palladacyclic intermediate. As far as we know, the developed protocol is the first general Pd-mediated methodology toward (Z)-configured homoallylic nitroalkanes with attractive functional group diversity.

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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