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Three different series of novel mononuclear arene-ruthenium(II) complexes containing amino-phosphine ligands, namely, [RuCl2{kappa 1(P)-2-Ph2PC6H4CH 2NHR}(eta6-arene)], [RuCl2{kappa 1(P)-3-Ph2PC6H4CH 2NHR}(eta6-arene)], and [RuCl2{kappa 1(P)-4-Ph2PC6H4CH 2NHR}(eta6-arene)] (arene = C6H6, p-cymene, 1,3,5-C6H3Me3, C6Me 6; R = iPr, tBu; all combinations), have been synthesized and fully characterized. These readily accessible species are efficient catalysts for the selective hydration of organonitriles into amides under challenging reaction conditions, i.e., pure aqueous medium in the absence of any cocatalyst, being much more active than their corresponding nonfunctionalized triphenylphosphine counterparts [RuCl2(PPh 3)(eta6-arene)]. The results obtained in this study indicate that the (amino-phosphine)ruthenium(II) complexes operate through a “bifunctional catalysis” mechanism in which the ruthenium center acts as a Lewis acid, activating the nitrile molecule, and the P-donor ligand acts as a Brnsted base, the pendant amino group generating the real nucleophile of the hydration process, i.e., the OH- group.

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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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Various complexes were shown to catalyze the polymerization of PhC=VCH 1 and the substituted arylacetylenes 2-8 at 25C in a stereoregular manner. The cis-oriented poly(arylacetylenes), so formed, were found to depolymerize selectively at 200-225C to the corresponding 1, 3, 5-triarylbenzene derivatives.

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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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We developed a series of new organic-inorganic hybrid hydrotalcite functionalized Ru catalytic systems. All the developed materials have been studied by FTIR, N2 physisorption, ICP-OES, XPS, NMR (1H, 13C, 29Si) and TEM analysis were performed to know the physiochemical behavior and structural morphology of functionalized hydrotalcite materials. XPS results strongly suggest that it involves the formation of N-Ru coordination bonds. We applied these well analyzed materials for CO2 hydrogenation reaction as catalyst (with and without ionic liquid medium). We found that Ru metal containing functionalized hydrotalcite materials were highly active and stable (in terms of catalyst leaching and recycling). The heterogeneous catalyst can be easily recovered and reused 8 times without significant loss of catalytic activity and selectivity, which is a better green alternative for practical applications.

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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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Several chiral and unsymmetrical tridentate [NNP]-type ligands with sp 2-N and sp3-N were synthesized from monosulfonamide of (1R, 2R)-1,2-diaminocyclohexane and 2-(diphenylphosphino)benzaldehyde. Their ruthenium(II) complexes have been used in the enantioselective asymmetric hydrogen transfer reduction of acetophenone in 2-propanol with selectivities in the range 14-99% e.e. The good enantioselectivity with the ligands with sp 2-N and sp3-N is believed to be due to formation of hexacoordinated complexes with a 2:1 ligand to metal ratio.

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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 palladium-iminophosphine complex was found to catalyze the homocoupling reaction of alkynylstannanes using allyl acetate as an oxidant, whereas aryl- and alkenylstannanes were oxidatively homocoupled with air.

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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 application of homogeneously soluble catalysts is limited by the recovery in cases where the price of the catalyst is high. Biological catalysts, enzymes, can be efficiently recycled by means of an ultrafiltration membrane due to their high molecular weight, for example, in the continuously operated membrane reactor. In order to transfer this principle to chemical catalysis, we have attached a transfer hydrogenation catalyst, first invented by Gao and Noyori, to a polymer. The resulting homogeneously soluble, polymer-bound catalyst (chemzyme) can now be retained by ultrafiltration membranes like enzymes. On applying this catalyst in continuously operated membrane reactors, a continuous isopropoxide dosage is necessary in order to compensate deactivation caused by water residues in the feed stream. Thus, high space-time yields up to 578 g L-1 d-1 and enantioselectivities up to 94% can he achieved. These results were compared to an enzyme catalyzed system consisting of a carbonyl reductase that also utilizes 2-propanol as a hydrogen source for the cofactor regeneration of NADH.

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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 new Ag2CO3/CA-AA-amidphos complexes have been demonstrated as highly efficient multifunctional catalysts in the asymmetric 1,3-dipolar cycloaddition of azomethine ylides. Under optimal conditions, highly functionalized endo-4 pyrrolidines were obtained with excellent yields (up to 99% yield) and enantioselectivities (up to 96% 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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Synthesis and characterization of hydridoirida-beta-diketones were discussed. Reaction of [{Ir(Cod)Cl}2] (Cod = 1,5-cyclooctadiene) with o-(Diphenylphosphino)benzaldehyde was performed and studied. Results showed the formation of acylhydride complexes that contain acylphosphine chelates.

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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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Chemistry is an experimental science, and the best way to enjoy it and learn about it is performing experiments.Introducing a new discovery about 50777-76-9, Name is 2-(Diphenylphosphino)benzaldehyde, name: 2-(Diphenylphosphino)benzaldehyde.

New chiral ferrocenyldiphosphine ligands (R)-(S)-3 and (R)-(S)-4 were prepared. The ligands were employed in Ru(II) catalyzed asymmetric transfer hydrogenation of ketones to give corresponding secondary alcohols. Up to 99% conversion with 90% e.e. was obtained on Ru(DMSO)4Cl2/4 in transfer hydrogenation of acetophenones with propan-2-ol.

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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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We describe here the synthesis and structural characterization of two new classes of ambiphilic, N-boryl imine ligands, wherein boron is associated with a Lewis basic imine nitrogen. These ligands can be easily generated in two steps from the corresponding pyridinyl- and phosphinyl-tethered aldehydes. 11B NMR analysis suggests the association of the Lewis acidic boron to either the pyridine unit or via intermolecular acid/base interactions with the imine. Both of these ligands can coordinate to palladium, and their structures were confirmed by X-ray crystallography..

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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