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Reactions of silver(I) chloride or nitrate with 2-(diphenylphosphano) benzaldehyde (dppbza) in 1:2 molar ratio afforded mononuclear complexes of the type [AgX(dppbza)2], whereas treatment of these compounds with equimolar amounts of pyridine-2-thione or 4,6-dimethylpyrimidine-2-thione gave rise to the formation of mixed-ligand complexes of the formula [Ag(dppbza) 2(thione)2]NO3 and [AgCl(dppbza)(thione)] 2, respectively. The molecular structure of [Ag(dppbza) 2(NO3)] has been established by single-crystal X-ray diffraction. The complex features a strongly distorted tetrahedral Ag(I) center surrounded by two phosphane P atoms and two O atoms from the nitrate anion. The new compounds show intense emission in the solid state and in solution at ambient temperature.

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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 synthesis of new hydrolytically stable oxime ether ligands by condensation of various aldehydes with O-beta-D-glucopyranosylhydroxylamine 1 or O-beta-D-galactopyranosylhydroxylamine 4 is described. After peracetylation of the hydroxyl groups, ligands soluble in organic solvents were obtained. The ligands have been tested in transition metal-catalysed reactions. Phosphorus-containing ligands gave high yields in palladium-catalysed allylic alkylation and rhodium-catalysed hydrosilylation reactions although the enantioselectivities were low. A 1,3-diphenylallyl-palladium(II) complex of ligand 2b was prepared and its structure was established by X-ray diffraction analysis.

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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 copper(I) halides complexes present a large structural variety and have numerous technological applications. In this work we have prepared two new copper(I) complexes with N-donor and P-donor ligands [CuI(2-(diphenylphosphino)benzaldehyde)2] (1), [CuI(2-(diphenylphosphino)benzaldehyde) (acetonitrile)]2 (2) from CuI as starting material. The complexes were characterized by elemental analysis, IR spectroscopy and crystallographic studies. Compound 1 crystallizes in a monoclinic C2/c space group. It is a monomer with a P-donor ligand bound with copper(I) in a distorted triangular planar geometry. Compound 2 crystallizes in monoclinic P21/c space group. It has two molecules of the P-donor ligand and two molecules of the N-donor ligand in trans configuration, forming a dimer with two bridging iodides. The Cu(I) atom is four coordinated in trigonal pyramidal geometry with tau4 value of 0.85. The bond distances are 2.5050(6)-2.7090(6) A for Cu?I, 2.044(4) A for Cu?N and 2.2489(8)-2.2528(8) A for Cu?P.

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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 novel chiral phosphine-imine ligands have been prepared by a two-step transformation from chiral alpha-phenylethylamine. The resulting chiral ligands were found to be effective for the palladium-catalyzed asymmetric allylic alkylation of 1,3-diphenylprop-2-en-1-yl pivalate with dimethyl malonate, in which up to 94% ee and 99% conversions were obtained. The results demonstrate that the chirality resided on the chelate ring of P-Pd-N complex is more effective for the transfer of the stereochemical information by comparison with the result obtained by Hashimoto and coworkers’ phosphine-imine ligand, in which the chirality lay in the outside of P-Pd-N chelate ring. The effect of solvent, base and substitutent in phosphine-imine ligand on this catalytic reaction is also 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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Octahedral and square-planar isothiocyanato complexes of Ni(II) with the condensation derivative of 2-(diphenylphosphino)benzaldehyde and Girard’s T reagent were synthesized and characterized by elemental analysis, IR spectroscopy and X-ray crystallography. Results of magnetic measurements for octahedral Ni(II) complex were also reported. In all the complexes the ligand is coordinated as tridentate via the phosphorus, the imine nitrogen and the carbonyl oxygen atoms while the remaining coordination positions are occupied with thiocyanato anions. Coordination of deprotonated phosphine ligand results in formation of square-planar complexes, while the octahedral complex was formed with protonated ligand. Reaction energetics with both forms of ligand were studied by the means of DFT and results were in complete agreement with experimental observations. Furthermore, ligand field splitting analysis gave the deeper insight in the relationship of the isolated complex coordination environment and protonation of the ligand.

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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 diphosphine ligand (1·HPF6), which is a potential precursor to a PCNHCP pincer, with a backbone containing two phenylene groups and a central bicyclic 4-aza-2-azoniabicyclo[3.2.1]oct-2-ene unit has been synthesised and coordinated to Pd(ii) and Pt(ii) to give trans-[M(kappa2-P,P?-1·H)Cl2]PF 6 where M = Pd (2) or Pt (3a). Single-crystal structure determinations of 2 and 3a show the complexes to be isostructural with the diphosphine coordinated in a trans-spanning fashion and the amidinium unit being protonated and non-coordinated. 2 and 3a react with CH3I to give the dimers trans-[Pd2(mu-1·H)2I4](PF 6)2, 6, and trans-[Pt2(mu-1·H) 2I4](PF6)2, 7, as the major products. This bridging mode of coordination of [1·H]+ is also seen in trans-[Rh2(mu-1·H)(1,5-COD)2Cl 2]PF6, 4, and [Pt2(mu-kappa2- 1·H)(dvdms)]PF6, 5. Upon treatment with KOtBu complexes 2 and 3a undergo deprotonation at the amidinium carbon to give trans-[M(kappa3-P,C,P?-1)Cl]PF6 where M = Pd (8), and Pt (9). The related trans-[Rh(kappa3-P,C,P?-1)(CO)] PF6 (10) is prepared directly from 1·HPF6 and Rh(acac)(CO)2: this and the palladium and platinum complexes 8 and 9 are isolated as isomeric mixtures as a consequence of a conformational isomerism. In situ deprotonation of 1·HPF6 followed by addition of Ag(CF3SO3) gave SAg- [Ag(kappa3-P,C,P?-1)(CF3SO3)], 11. Some preliminary studies of the reactivity of 2 and 8 in Suzuki-type reactions are reported and the Pt(0) system has been shown to be an active hydrosilylation catalyst.

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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 the field of catalytic hydrogenation and, more particularly, to the use of Ru complexes with tetradentate ligands having at least one amino or imino coordinating group and at least one phosphino coordinating group in hydrogenation processes for the reduction of esters or lactones into the corresponding alcohol or diol 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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Palladium(II) complexes containing phosphorus and nitrogen donor atoms (iminophosphine), dichlorido{N-[2-(diphenylphosphino)benzylidene]-2- trifluoromethylaniline}palladium(II) 1, dichlorido{N-[2-(diphenylphosphino) benzylidene]-3-trifluoromethylaniline}palladium(II) 2, dichlorido{N-[2- (diphenylphosphino)benzylidene]-2-methylaniline}palladium(II) 3, dichlorido{N-[2-(diphenylphosphino)benzylidene]-3-methylaniline}palladium(II) 4 have been successfully synthesized and fully characterized by FT-IR and NMR (1H, 31P, 19F, and 13C) spectroscopy techniques. These complexes were first step tested in the reaction of bromobenzene and styrene to determine the optimal coupling reaction conditions and then successfully applied as catalysts for Heck cross-coupling reactions of activated and deactivated aryl bromides with styrene derivatives and several acrylates. Copyright

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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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Three new iminophosphines containing pinacol-derived boronate esters have been prepared and ligated to dichloridoplatinum( II) fragments. All compounds have been characterized fully, including an X-ray diffraction study carried out for the platinum complex 8, which is derived from 4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)aniline. These three new platinum complexes, along with the non-boron containing control, have been examined for their initial cytotoxic properties against two glioma cell lines using the MTT method.

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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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Poly(phosphorhydrazone) dendrimers constitute a versatile class of dendrimers, which can be functionalized at will at all levels of the structure (surface, core, branches) with various types of ligands (mono-, bi-, multi-dentate ligands), suitable for the complexation of different types of metals, including transition metals, lanthanides, or alkaline earths. This review is organized depending on the type of ligands. The properties of the corresponding complexes have been studied in many cases, and will be given. Most of the properties concern catalysis; a positive dendrimeric effect has been observed in many cases when the generation of the dendrimer increases. In many cases it is possible to recover the catalyst and to reuse it (up to ten times with the same efficiency). Other properties concern the field of materials, with the functionalization of the surface of electrodes, in particular with ferrocene-containing dendrimers, or the elaboration of metallic nanoparticles, and even their organization in dendritic networks. A single example of property in the field of biology is given, but it constitutes a promising result as anti-proliferative agents against cancerous cells.

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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