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Electron transfer from hexameric copper hydrides

The octahedral core of 84-electron LCuH hexamers does not dissociate appreciably in solution, although their hydride ligands undergo rapid intramolecular rearrangement. The single-electron transfer proposed as an initial step in the reaction of these hexamers with certain substrates has been observed by stopped-flow techniques when [(Ph3P)CuH]6 is treated with a pyridinium cation. The same radical cation has been prepared by the oxidation of [(Ph3P)CuH]6 with Cp* 2Fe+ and its reversible formation observed by cyclic voltammetry; its UV-vis spectrum has been confirmed by spectroelectrochemistry. The 48-electron trimer [(dppbz)CuH]3 has been prepared by use of the chelating ligand 1,2-bis(diphenylphosphino)benzene (dppbz).

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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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Preparation of Hybrid Bidentate Phosphine Ligands by Reduction of Their Benzyl- or Phenyl-phosphonium Salts. X-Ray Crystal Structure of 2-Aminophenyltriphenylphosphonium Tetrachloronickelate(II)

The 2-substituted phenylphosphine bidentate hybrid ligands, 2-aminophenyl-, 2-methylaminophenyl-, 2-hydroxyphenyl- and (2-amino-3-methylphenyl)-diphenylphosphine, (1a-d), respectively, and 2-aminophenylmethylphenylphosphine, (1e), were synthesized by reduction of their phenylphosphonium halides, (2a-e)X (X = Cl or Br), with sodium naphthalenide in tetrahydrofuran at -68 deg, or electrochemically at a mercury cathode.The phosphonium salts were prepared by reaction of triphenylphosphine with aryl halide and anhydrous nickel halide at 200 deg.X-Ray diffraction of (2a)2 showed it to have monoclinic space group P21/n, a 10.657(4), b 20.966(3), c 20.422(6) Angstroem, beta 101.33(2) deg and Z 4.The structure was refined by a full-matrix least-squares procedure to a final R 0.050 for 3534 reflections with I > 2.5?(I).

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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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Phosphastannirane: A phosphorus/tin(II) lewis pair that undergoes alkyne and alkene addition

Bermuda triangle: The first molecule containing a cyclic three-membered Sn-C-P ring has been synthesized and characterized. This SnII-P Lewis pair reacts at room temperature with alkynes and pentene to give the five-membered cyclic addition products. In the case of pentene, this reaction is reversible at room temperature. Trip=2,4,6-iPr3C6H 2. 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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Readily available air- and moisture-stable dimeric chloro-bridged CN-, CS- and CP-cyclopalladated complexes with the (sp2)C-Pd bond react with 4.5 equiv. of KPPh2 in THF to give the corresponding P,N-, P,S- and P,P-bidentate ligands in 35-63% yield. The phosphination method is applicable to five- and six-membered palladacycles derived from (S)-N,N-dimethyl-1- phenylethylamine, (S)-4-tert-butyl-2-phenyl-2-oxazoline, benzyl methyl sulfide, benzyldiphenylphosphine, 2-benzylpyridine and N,N-dimethylbiphenyl-2-amine. The reaction of 1.2 equiv. of KPPh2 with the SCS-pincer cyclopalladated complex obtained from 1,3-bis(methylthiomethyl)benzene provided the corresponding S,P,S-tridentate ligand in 49% yield.

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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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Synthesis of air-stable zwitterionic 2-phosphiniminium-arenesulfonates

Efficient synthetic methodology for preparation of 2-phosphiniminium-5- methylbenzenesulfonate zwitterions is reported. Staudinger reaction between phosphines and n-propyl 2-azido-5-methylbenzenesulfonates followed by sulfonate ester deprotection using pyridinium tetrafluoroborate/pyridine afforded the zwitterions in excellent yields. This new route directly accesses ortho-substituted-arenesulfonate ligands that incorporate a phosphinimine, a strong sigma-donor.

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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 ruthenium catalyst with simple triphenylphosphane for the enantioselective hydrogenation of aromatic ketones

An efficient Ru catalyst constructed from simple and commercially available triphenylphosphane and enantiopure (1S,1?S)-1,1?-biisoindoline (BIDN) was applied to the asymmetric hydrogenation of aromatic ketones. A range of simple aromatic ketones could be hydrogenated with good to excellent enantioselectivities (up to 95% ee). An appropriate enantioselective transition state was proposed to explain the high enantioselectivity obtained with this catalytic system. This study represents the first example to establish a practical Noyori-type catalyst with a simple achiral monophosphane for highly enantioselective hydrogenation. Keep it simple: An efficient Ru catalyst constructed from simple and commercially available triphenylphosphane and enantiopure (1S,1?S)-1,1?-biisoindoline (BIDN) was applied to the asymmetric hydrogenation of aromatic ketones. A range of simple aromatic ketones could be hydrogenated with good to excellent enantioselectivities (up to 95% ee).

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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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Efficient, phosphine-directed ortho C?H borylation of arylphosphine derivatives was achieved using Ru catalysts for the first time. The reaction is applicable to various tertiary arylphosphine and arylphosphinite derivatives to give (o-borylaryl)phosphorus compounds in high yields. This reaction enables easy access to a variety of functionalized phosphine ligands and ambiphilic phosphine boronate compounds, thus realizing a new late-stage modification of phosphorus compounds.

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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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An ionic iridium(III) complex [Ir(F2dpyb)(bzdpp)2Cl][OTf] with 1,3-difluoro- 4,6-di(2-pyridinyl) benzene (F2dpybH) terdentate ligand and benzyldiphenylphosphine (bzdpp) ligand was synthesized and characterized. The structure of iridium complex was verified by single-crystal X-ray crystallography. It crystallizes in monoclinic, space group P21/n with a = 14.3654(7), b = 23.0026(10), c = 15.7964(7) A,beta = 97.6029(11), V = 5173.9(4) A3, Z = 4, F(000) = 2552, Dc = 1.645 Mg/m3, Mr = 1281.49 and mu = 0.071 mm-1. The UV-vis absorption and phosphorescence of the complex were discussed. The complex was ‘aggregation induced emission (AIE)’ active. It exhibited no emission in CH2Cl2 solution but strong blue-green emission in solid state under ultraviolet light excitation. The complex emitted a strong phosphorescence centered at 493 nm when doped in PMMA. Its lifetime is 0.755 mus and quantum yield is approximately 0.134.

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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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The trihalophosphane complexes LnM-PHal3 (LnM = Cp(CO)2Mn, (CO)5Cr, (CO)5W; Hal = Cl, Br), upon treatment with Co2(CO)8, mainly yield clusters of the type Co3(CO)9(mu4-P)MLn with the (mu3-P)Co3(CO)9 unit acting as ligand.The analogous arsenic compound Co3(CO)9(mu4-As)Cr(CO)5 is obtained from the arsinidene complex <(CO)5Cr>2As-Cl with NaCo(CO)4.In addition to the syntheses and reactions of these clusters several reactions leading to clusters with mu4-P-, mu4-As, mu4-PR- and mu2-PR2 groups by reductive dehalogenation of coordinated halophosphanes are reported.The different types of compounds are documented by six X-ray-structure analyses.

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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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Benz-azaphosphininones (1) are synthesized by intramolecular cyclocondensation of phosphine imides (2) in the presence of base.

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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