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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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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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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

Some scientific research about 1,1-Bis(diphenylphosphino)ferrocene

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The reaction of [RhCl(PPh3)3] with [9]aneS3 (1,4,7-trithiacyclononane) and NH4PF6 provides [Rh(PPh3)2([9]aneS3)PF6, which undergoes ligand subsitution and oxidative-addition reactions and effectively catalyzes the demercuration of bis(alkynyl)mercurials.

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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 reaction of the Schiff base ligand 3,4-(OCH2O)C6H3C(H)=NCH2[3,4- (OCH2O)C6H3] (a) with Pd(OAc)2 yields two endocyclic cyclometallated compounds: [Pd{3,4-(OCH2O)C6H2C(H)=NCH2 [3,4-(OCH2O)C6H3]-C2,N}(mu-O 2CMe)]2 (C2,N-bonded) (1a), and [Pd{3,4-(OCH2O)C6H2C(H)=NCH2 [3,4-(OCH2O)C6H3]-C6,N}(mu-O 2CMe)]2 (C6,N-bonded) (1b), which may be separated by fractional crystallization. The corresponding cyclopalladated dimers with bridging chloride ligands, 2a, 2b, have been prepared by a metathesis reaction with aqueous sodium chloride. Treatment of the latter compounds with tertiary phosphines in the appropriate molar ratio gave the mono and dinuclear compounds, 3a-8a and 3b-5b, respectively. The structure of compound 1a has been determined by X-ray diffraction analysis. The molecular configuration is a dimeric form of the anti isomer with the cyclopalladated moieties in an ‘open-book’ arrangement linked by two acetate bridging ligands.

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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 pincer complexes [MX(CNN)(PP)] (M = Ru, Os; X = Cl, OTf; HCNN = 1-(6-arylpyridin-2-yl)methanamine; PP = diphosphine) have proven to efficiently catalyze both racemization and deuteration of alcohols in the presence of a base. Chiral alcohols have been racemized at 30-50 C using 1 mol% of Ru or Os pincer complexes and 5 mol% of KOtBu in 2-propanol. Primary and secondary alcohols are efficiently deuterated at the alpha position, with respect to the OH group, using 2-propanol-d8 as solvent with Ru or Os pincer complexes and KOtBu at 30-50 C. For secondary alcohols incorporation of deuterium at the beta position has also been observed. In 2-propanol-d 8 the pincer complexes catalyze the simultaneous deuteration and racemization of (S)-1-phenylethanol, the two processes being strictly correlated. For both reactions much the same activity has been observed with the Ru and Os complexes. The pincer complexes display a superior activity with respect to the related compounds [MCl2(NN)(PP)] (NN = bidentate amine or pyridine ligand). The synthesis of the new complexes [MCl(CNN)(PP)] (M = Ru, 2, 4 and Os, 6, 7; PP = dppb, dppf) and [Ru(OTf)(CNN)(dppb)] (3) is also reported. The Royal Society of Chemistry 2011.

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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 syntheses of [3]- and [4]cyclo-9,9-dimethyl-2,7-fluorenes ([3] and [4]CFRs), cyclic trimer, and tetramers of 9,9-dimethyl-2,7-fluorene (FR), respectively, were achieved by the platinum-mediated assembly of FR units and subsequent reductive elimination of platinum. A triangle-shaped tris-platinum complex and a square-shaped tetra-platinum complex were obtained by changing the platinum ligand. The structure of the triangle complex was unambiguously determined by X-ray crystallographic analysis. Reductive elimination of each complex gave [3] and [4]CFRs. Two rotamers of [3]CFR were sufficiently stable at room temperature and were separated by chromatography. The physical properties of the CFRs were also investigated theoretically and experimentally.

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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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Treatment of the functionalized Schiff base ligands with boronic esters 1a, 1b, 1c and 1d with palladium (II) acetate in toluene gave the polynuclear cyclometallated complexes 2a, 2b, 2c and 2d, respectively, as air-stable solids, with the ligand as a terdentate [C,N,O] moiety after deprotonation of the -OH group. Reaction of 1j with palladium (II) acetate in toluene gave the dinuclear cyclometallated complex 5j. Reaction of the cyclometallated complexes with triphenylphosphine gave the mononuclear species 3a, 3b, 3c, 3d and 6j with cleavage of the polynuclear structure. Treatment of 2c with the diphosphine Ph2PC5H4FeC5H4PPh2 (dppf) in 1:2 molar ratio gave the dinuclear cyclometallated complex 4c as an air-stable solid. Deprotection of the boronic ester can be easily achieved; thus, by stirring the cyclometallated complex 3a in a mixture of acetone/water, 3e is obtained in good yield. Reaction of the tetrameric complex 2a with cis-1,2-cyclopentanediol in chloroform gave complex 2c after a transesterification reaction. Under similar conditions complexes 3a and 3d behaved similarly: with cis-1,2-cyclopentanediol, pinacol or diethanolamine complexes 3c, 3b, 3g and 3f, were obtained. The pinacol derivatives 3b and 3g experiment the Petasis reaction with glyoxylic acid and morpholine in dichloromethane to give complexes 3h, and 3i, respectively.

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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

Some scientific research about 1,1-Bis(diphenylphosphino)ferrocene

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Novel mono- and didentate ferrocenylphosphines containing complexes, [Mo2(CO)6(dfpp)2(mu-pa)] (dfpp = diferrocenylphenylphosphine) and [Mo2(CO)6(mu-dppf)(mu-pa)], have been isolated and characterized by infrared and electronic spectroscopy, and cyclic voltammetry. For the [Mo2(CO)6(mu-dppf)(mu-pa)] complex a single crystal X-ray structure analysis evidences its double bridge nature and the asymmetry of the bridging ligands due to steric constraints. In the visible region, the new compounds show strong solvatochromic bands and this effect has been evaluated by using the E*MLCT parameter. The redox behaviour of the complexes involves molybdenum and ferrocene-based oxidations and pa-based reductions. The results are compared to the previously characterized analogous complexes based on the related ligands triphenylphosphine and 1,2-bis(diphenylphosphino)ethane.

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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