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Treatment of the complexes [MCl2(DPPF)] (M=Pt or Pd) {readily prepared in high yield from [MCl2(DMSO)2] (M=Pt (cis-) or Pd (trans-) and DPPF in CHCl3} with two molar proportions of AgNO3 in H2O did not give the expected cation [M(DPPF)(H2O)2] 2+ in solution. Instead the unusual homobimetallic bridged complex [{M(mu-OH)(DPPF)}2](NO3)2 was formed as an insoluble solvolysis solid product. Hence, carboxylation by addition of carboxylate anions to the solution cannot be carried out by this method. In contrast, the complex [PtCl2(DPPF)] reacted readily with two molar proportions of AgOAc or one of Ag2{1,1?-(OOC)2fc} (fc=ferrocene-2H) in acetone to give the corresponding carboxylato complexes. Other carboxylato complexes were obtained from the reaction of the complexes [MCl2(DPPF)] and the K-salts of e.g. (COOH)2, CH2(COOH)2, and CH2CH2CH2C(COOH)2 in H2O. With few exceptions, neither the K- nor the Ag-salts of the acids Me3CCOOH and C6H11COOH react completely with [MCl2(DPPF)] in aqueous or non-aqueous solutions. However, the required products were obtained by displacement of DMSO from the corresponding carboxylato complexes by DPPF in CHCl3. All of the new carboxylato complexes and the solvolysis products were characterized physicochemically and spectroscopically. The X-ray structures of [Pt{(OOC)2}(DPPF)] and of [PtCl(NO3)(DPPF)] were determined, to obtain some additional information on the coordination mode of the unsymmetrical DPPF ligand in this type of 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

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1,2,4-Trimethyl-cyclohexadiene reacts with RuCl3·nH 2O in refluxing ethanol to afford quantitatively [RuCl 2(1,2,4-C6H3Me3)]2 (1), the coordination of 1,2,4-trimethylbenzene to the ruthenium atom introducing planar chirality at the eta6-arene ligand. The dinuclear complex 1 reacts with two equivalents of triphenylphosphine (PPh3) to give quantitatively, as a racemic mixture of enantiomers, [RuCl2(1,2,4- C6H3Me3)(PPh3)] (2), the structure of which has been determined by a single-crystal X-ray structure analysis of (rac)-2. Similarly, 1 reacts with two equivalents of the enantiopure phosphine (1S,2S,5R)-(+)-neomenthyldiphenylphosphine (nmdpp) to afford in good yield [RuCl2(1,2,4-C6H3Me3)(nmdpp)] (3) as a mixture of diastereoisomers, from which the isomer 3a was isolated by crystallisation. A single-crystal X-ray structure analysis of 3a allowed the determination of the absolute configuration at the planar chiral eta 6-arene moiety. Finally, complex 1 reacts with one equivalent of the diphosphine ligand 1,1?-bis(diphenylphosphino)ferrocene (dppfc) to give the heteronuclear complex [RuCl2(1,2,4-C6H 3Me3) (dppfc)RuCl2(1,2,4-C6H 3Me3)] (4). All complexes were fully characterised by elemental analysis, mass spectrometry, NMR and IR spectroscopies.

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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 natural bite angle of bidentate phosphane ligands influences the isomer distribution (syn and anti) in (1-methylallyl)(bisphosphane)Pd OTf complexes. It was found (31P- and 1H-NMR studies) that the syn/anti ratio changes from 12 (dppp) to 1.3 (sixantphos). Molecular orbital calculations [PM3(tm) level] indicate that for ligands inducing a large bite angle, the phenyl rings of the ligand embrace the allyl moiety, thus influencing the syn/anti ratio. This bite-angle effect on the syn/anti ratio is transferred to the regioselectivity in stoichiometric allylic alkylation. Ligands inducing large bite angles direct the regioselectivity towards the formation of the branched product 2. Catalytic alkylation of (E)-2-butenyl acetate showed that for ligands with a small bite angle the regioselectivity of the catalytic and stoichiometric alkylation are in good agreement. This correspondence is worse for ligands with a larger bite angle, which is rationalised in terms of the relative rates of syn/anti isomerisation and alkylation. The ligand with the largest bite angle (sixantphos) gives the most active catalytic species.

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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 chemistry of the trinuclear sulfphonohydrazido-capped ruthenium clusters (mu2-H)Ru3(CO)9[mu3-eta2-H2NNS(O)2R] (R = Mes or Tol) was studied. Protonation occurs at the Ru3 metal framework to give a cationic dihydrido cluster, monosubstitution of a carbonyl with phosphine ligands takes place at the ruthenium atom coordinated to the NH2 group of the hydrazido cap and, for the disubstitution with diphosphine ligands, two different coordination modes are observed.

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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 series of ruthenium [NNN]- or [NCN]-type complexes (3?7) bearing PPh3 ancillary ligands have been synthesized from pyridine- or phenylene-bridged bis(triazoles) 1 and 2. In the case of [NNN]-pincer complex 3, an unusual and unexpected cis-orientation adopted by two sterically demanding PPh3 ligands was observed, and such configuration proved to be unchanged in solution for a long time. By contrast and as expected, the two phosphines are found to be trans to each other in the case of [NCN]-type pincer complex 4, but an oxidation of RuII center to RuIII occurred. Complex cis-3 underwent ligand exchanges leading to the formations of diphosphine derivatives 5 and 6. As a representative, cis-3 was treated with the base in isopropanol affording a mixture of Ru?hydrido complexes with various phosphine binding modes, one of which (trans-7) bearing two trans-standing phosphines has been successfully isolated and fully characterized. The catalytic performances of all newly synthesized Ru complexes have been examined and compared in transfer hydrogenations of ketones and enones, in which mono-phosphine complexes proved to be significantly superior to their diphosphine counterparts. The catalytic process proved to involve Ru?H key intermediates, but the trans-oriented Ru?H species is unlikely to be the main catalytic contributor. In particular, the best performer cis-3 exhibits high chemoselectivity in certain cases catalyzing alpha,beta-unsaturated ketones, whose behavior is quite different compared to most precedents.

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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 mild and effective method is described for 11C-labeling of peptides selectively at the N-terminal nitrogen or at internal lysine positions. The presented method relies on the use of specific biphosphine palladium?methyl complexes and their high reactivity towards amino-carbonylation of amine groups in the presence [11C]carbon monoxide. The protocol facilitates the production of native N-11C-acetylated peptides, without any structural modifications and has been applied to a selection of bioactive peptides.

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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 oxidative electrochemistry of a variety of homo- and bimetallic group VI metal carbonyl compounds containing 1,1?-bis(diphenylphosphino) ferrocene (dppf) with the general formulas M(CO)5(dppf) (1a-c), M(CO)4(dppf) (2a-c), and (CO)5M(dppf)M'(CO)5 (3a-f) (M, M’ = Cr, Mo, W) was investigated. The effect of the group VI metal and the coordination mode of the dppf ligand on the potential at which the oxidation of the group VI metals and the ferrocene backbone of dppf occurred was examined.

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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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Cyclic phosphonium anhydrides generated from bis-phosphine oxides and trifluoromethanesulfonic anhydride are shown as general coupling reagents in a dehydrative glycosylation reaction of C1-hemiacetals. This reaction protocol is characterized by a broad substrate scope and high yields, including reactions of O-, C-, N-, and S-based nucleophiles with furanose, pyranose, and deoxysugar donors.

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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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[NH4]2[MoS4] reacts with CuBr and [Bu4N]Br in the solid state to afford an intermediate product with proposed constitution [Bu4N]4[MoS4Cu6Br8] (1). Treatment of cluster (1) with an equal equivalent of dppf in CH3CN-DMF solution resulted in the formation of a pentanuclear cluster [MoS4(Cudppf)2]·2DMF·CH3CN (2). Cluster (2) crystallizes in the monoclinic space group P21/n with four formula units in a cell of dimensions a = 13.1267(8), b = 38.040(2), c = 15.2661(9) A, and beta = 97.6030(10). Refinement by full-matrix least-squares techniques gave final residuals R = 0.0567 and wR = 0.1679. The structure of (2) can be described as two (Cudppf)+ units linked through MoS42- to form a pentanuclear folding-ruler array. Reaction of (1) with excess Ph2PPy in CH3CN solution resulted in the formation of a trinuclear cluster [MoS4Cu2(Ph2PPy)4] (3). Cluster (3) crystallizes in the tetragonal space group I41/a with cell constants a = 17.427(6), b = 17.427(6), c = 21.344(5) A, and Z = 4. Final residuals R = 0.0337 and wR = 0.0616. The structure of (3) is built up from two Cu(Ph2PPy)2+ units bridged by a MoS42- ligand to form a trinuclear symmetrical linear molecule. Clusters (2) and (3) exhibit strong optical absorption (effective a2 = 1.6 × 10-9 m W-1 (2) and 1.2 × 10-9 m W-1 (3)) and optical self-defocusing effects (n2 = -1.35 × 10-17 m2 W-1 (2) and -6.84 × 10-17 m2 W-1 (3)), their limiting thresholds were determined to be 0.35 J cm-2 (2) and 0.65 J cm-2 (3), which are about four and two times, respectively, better than that of C60.

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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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Reaction of RuH2CO(PPh3)3 with tetrafluorosuccinic acid at 100C gave rise to the formation of the dinuclear bis(tetrafluorosuccinate)-bridged Ru(II) complex 2, containing two water ligands. Exchange of the PPh3 in complex 2 with various diphosphine ligands afforded a series of analogous complexes 3. Reaction of the latter with 1-phenylethanol at 130C or with 2-propanol/Et3N at room temperature furnished the dinuclear dihydrido-bridged Ru(II) complexes 4. Complexes 2 and 4 were characterized by X-ray diffraction analysis. Both bis(tetrafluorosuccinate)-bridged complexes 3 and dihydrido-bridged complexes 4 catalyze the acceptorless dehydrogenation of 1-phenylethanol to acetophenone and dihydrogen with good yields and excellent selectivity under relatively mild conditions in the absence of acid or base. A tentative catalytic cycle for the dehydrogenation of secondary alcohols by Ru(II) complexes of type 3 is 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