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Complexes [Pd{C,N-Ar{C(Me)NOH}-2}(mu-Cl)]2 (1) with Ar = C6H4, C6H3NO2-5 or C 6H(OMe)3-4,5,6, were obtained from the appropriate oxime, Li2[PdCl4] and NaOAc. They reacted with neutral monodentate C-, P- or N-donor ligands (L), with [PPN]Cl ([PPN] = Ph 3PNPPh3), with Tl(acac) (acacH = acetylacetone), or with neutral bidentate ligands NN (tetramethylethylenediamine (tmeda), 4,4?-di-tert-butyl-2,2?-bipyridine (tBubpy)) in the presence of AgOTf or AgClO4 to afford complexes of the types [Pd{C,N-Ar{C(Me)NOH}-2}Cl(L)] (2), [PPN][Pd{C,N-Ar{C(Me)NOH}-2}Cl2] (3), [Pd{C,N-Ar{C(Me)NOH}-2}(acac)] (4) or [Pd{C,N-Ar{C(Me)NOH}-2}(NN)]X (X = OTf, ClO4) (5), respectively. Complexes 1 reacted with bidentate NN ligands in the presence of a base to afford mononuclear zwitterionic oximato complexes [Pd{C,N-Ar{C(Me)NO}-2}(NN)] (6). Dehydrochlorination of complexes 2 by a base yielded dimeric oximato complexes of the type [Pd{mu-C,N,O-Ar{C(Me)NO} -2}L]2 (7). The insertion of XyNC into the Pd-Caryl bond of complex 2 produced the mononuclear iminoaryloxime derivative [Pd{C,N-C(NXy)Ar{C(Me)NOH}-2}Cl(CNXy)] (8) which, in turn, reacted with [AuCl(SMe2)] to give [Pd{mu-N,C,N-C(NXy)Ar{C(Me)NOH}-2}Cl] 2 (9) with loss of XyNC. Some of these complexes are, for any metal, the first containing cyclometalated aryloximato (6, 7) or iminoaryloxime (8, 9) ligands. Various crystal structures of complexes of the types 2, 3, 6, 7, 8 and 9 have been determined.

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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

Final Thoughts on Chemistry for 2-(Diphenylphosphino)benzoic acid

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A series of new multifunctional ligands based on the benzotriazole unit has been synthesized by condensation of hydroximethylbenzotriazole with carboxylic acid derivatives of pyridine, triphenylphosphine, ferrocene and thiophene. The coordination properties of these ligands towards cobalt, rhodium and iridium have been studied.

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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 first photosensitizer-free visible light-driven, gold-catalyzed C?C cross-couplings of arylboronic acids and aryldiazonium salts are reported. The reactions can be conducted under very mild conditions, using a catalytic amount of tris(4-trifluoromethyl)phosphinegold(I) chloride [(4-CF3-C6H4)3PAuCl] with methanol as the solvent allowing an alternative access to a variety of substituted biaryls in moderate to excellent yields with broad functional group tolerance. (Figure 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

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Application of 13885-09-1, Chemistry can be defined as the study of matter and the changes it undergoes. You’ll sometimes hear it called the central science because it is the connection between physics and all the other sciences, starting with biology.13885-09-1, Name is 2-(Diphenylphosphino)biphenyl, molecular formula is C24H19P. In a patent, introducing its new discovery.

The direct and scalable electroreduction of triphenylphosphine oxide (TPPO)-the stoichiometric byproduct of some of the most common synthetic organic reactions-to triphenylphosphine (TPP) remains an unmet challenge that would dramatically reduce the cost and waste associated with performing desirable reactions that are mediated by TPP on a large scale. This report details an electrochemical methodology for the single-step reduction of TPPO to TPP using an aluminum anode in combination with a supporting electrolyte that continuously regenerates a Lewis acid from the products of anodic oxidation. The resulting Lewis acid activates TPPO for reduction at mild potentials and promotes P-O over P-C bond cleavage to selectively form TPP over other byproducts. Finally, this robust methodology is applied to (i) the reduction of synthetically useful classes of phosphine oxides, (ii) the one-pot recycling of TPPO generated from a Wittig reaction, and (iii) the gram-scale reduction of TPPO at high concentration (1 M) with continuous product extraction and in flow at high current density.

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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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Addition of ligands to [Pd(eta3-RCH-CH-CH2) (mu-Cl)]2 or chloride ions to cationic [(eta3 -RCH-CH-CH2)PdL2] +BF4 – induces the formation of neutral complexes eta1 -RCH-CH-CH2-PdClL 2 (R=H with L=(4-Cl-C6 H4) 3P, (4-CH3-C6H 4) 3P, (4-CF3-C6 H4) 3P or L2=1,2-bis(diphenylphosphino) butane (dppb), 1,1?-bis(diphenylphosphino)ferrocene (dppf); R=Ph with L=(4-Cl-C6H4)3P), instead of the expected cationic complexes [(eta3-RCH-CH- CH2) PdL2]+Cl-. In the presence of chloride ions, the reaction of morpholine with the cationic complexes [(eta 3-allyl)Pd (PAr3)2]+BF 4- (Ar=4-Cl-C6H4, 4-CH 3- C6H4) goes slower and involves both cationic [(eta3-allyl)Pd(PAr3)2] + and neutral eta1-allyl-PdCl(PAr3) 2 complexes as reactive species in equilibrium with Cl-. The cationic complex is more reactive than the neutral one. However, their relative contribution in the reaction strongly depends on the chloride concentration, which controls their relative concentration. The neutral eta1-allyl-PdCl(PAr3) 2 may become the major reactive species at high chloride concentration. Consequently, [Pd(eta3-allyl)(mu-Cl)] 2 associated with ligands or cationic [(eta3 -allyl) PdL2]+BF4-, used indifferently as precursors in palladium-catalyzed allylic substitutions, are not equivalent. In both situations, the mechanism of the Pd-catalyzed allylic substitution depends on the concentration of the chloride ions, delivered by the precursor or purposely added, that determines which species, [(eta3-allyl) PdL2]+ or/and eta1-allyl- PdClL2 are involved in the nucleophilic attack with consequences on the rate of the reaction and probably on its regioselectivity. Consequently, the chloride ions of the catalytic precursors [Pd(eta3-allyl)(mu-Cl)] 2 must not be considered as ‘innocent’ 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

Final Thoughts on Chemistry for Di(naphthalen-2-yl)phosphine oxide

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Electric Literature of 78871-05-3, Chemistry can be defined as the study of matter and the changes it undergoes. You’ll sometimes hear it called the central science because it is the connection between physics and all the other sciences, starting with biology.78871-05-3, Name is Di(naphthalen-2-yl)phosphine oxide, molecular formula is C20H15OP. In a patent, introducing its new discovery.

A newly developed aqueous system with acid and phosphide was introduced in which odorless and stable sodium arylsulfinates can in situ generate arylsulfenyl radicals. These radicals have high reactivity to react with alkynes, alkenes, and H-phosphine oxides for the synthesis of alkyl and alkenyl sulfides and phosphonothioates. The control experiments and quantum calculations are also performed to gain insights into the generation mechanism of arylsulfenyl radicals. Notably, the chemistry is free of thiol odors, organic solvents, and metals.

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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

Discovery of Tri-p-tolylphosphine

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A series of brightly luminescent, three-coordinate copper(i) arylamidophosphine complexes have been prepared from readily available precursors in high yield. Emission maxima span 102 nm in the visible spectrum from 461 (blue) to 563 nm (yellow) while photoluminescence quantum yields range from 0.11 to 0.24 in fluid solution at room 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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C-H Arylation of olefins by triarylphosphines via C-P bond cleavage has been achieved with either Pd0 or PdII catalysts. A variety of olefins and triarylphosphines are tolerated, and we inferred that both Pd0 and PdII could function directly without pre-oxidation or pre-reduction.

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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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Iron hydride complexes of the general formula P2Fe(NO)CO)H are highly active catalysts for the hydrosilylation of aldehydes or ketones and phosphine oxides. Depending on the solvent, the in situ reduction of the phosphine oxide can be faster than the corresponding hydrosilylation of a carbonyl group. This unusual activity was used within the context of catalytic Wittig olefination. Picture perfect: Iron hydride complexes of the general formula P2Fe(NO)CO)H are highly active catalysts for the hydrosilylation of aldehydes or ketones and phosphine oxides. Depending on the solvent, the in situ reduction of the phosphine oxide can be faster than the corresponding hydrosilylation of a carbonyl group. This unusual activity is used within the context of catalytic Wittig olefination. EWG=Electron-withdrawing 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

Discovery of 2′-(Dicyclohexylphosphino)-N,N-dimethyl-[1,1′-biphenyl]-2-amine

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We report a general palladium-catalyzed beta-arylation of Boc-piperidines, which yields a variety of valuable 3-arylpiperidines in a simple and direct manner. The beta- vs. alpha-arylation selectivity was controlled by the ligand, with flexible biarylphosphines providing mainly the desired beta-arylated products whereas more rigid biarylphosphines mainly furnished the more classical alpha-arylated products. The computed reaction mechanism (DFT), studied from the common alpha-palladated intermediate, indicated that the reductive elimination steps leading to the alpha- and beta-arylated products are selectivity-determining. Moreover, the experimental trend obtained with different ligands was well reproduced by the calculations.

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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