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The reaction of [Fe2(CO)6(mu-toluene-3, 4-benzenedithiolate)] 1 and bidentate diphosphine, 1, 1?-bis(diphenylphosphino)ferrocene (dppf) has been studied. New complexes obtained have been characterized by various spectroscopic techniques as bioinspired models of the iron hydrogenase active site. The crystal structure of [Fe2(CO)5(kappa 1-dppfO)(mu-toluene-3, 4-benzenedithiolate)] 4 is reported. [Figure not available: see fulltext.]

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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

Extended knowledge of (9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine)

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The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.161265-03-8, Name is (9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine), molecular formula is C39H32OP2. In a Article,once mentioned of 161265-03-8, name: (9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine)

Herein, [Cu(P^P)(N^N)][PF6] complexes (P^P=bis[2-(diphenylphosphino)phenyl]ether (POP) or 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (xantphos); N^N=CF3-substituted 2,2?-bipyridines (6,6?-(CF3)2bpy, 6-CF3bpy, 5,5?-(CF3)2bpy, 4,4?-(CF3)2bpy, 6,6?-Me2-4,4?-(CF3)2bpy)) are reported. The effects of CF3 substitution on their structure as well as their electrochemical and photophysical properties are also presented. The HOMO?LUMO gap was tuned by the N^N ligand; the largest redshift in the metal-to-ligand charge transfer (MLCT) band was for [Cu(P^P){5,5?-(CF3)2bpy}][PF6]. In solution, the compounds are weak yellow to red emitters. The emission properties depend on the substitution pattern, but this cannot be explained by simple electronic arguments. Among powders, [Cu(xantphos){4,4?-(CF3)2bpy}][PF6] has the highest photoluminescence quantum yield (PLQY; 50.3 %) with an emission lifetime of 12 mus. Compared to 298 K solution behavior, excited-state lifetimes became longer in frozen Me-THF (77 K; THF=tetrahydrofuran), thus indicating thermally activated delayed fluorescence (TADF). Time-dependent (TD)-DFT calculations show that the energy gap between the lowest-energy singlet and triplet excited states (0.12?0.20 eV) permits TADF. Light-emitting electrochemical cells (LECs) with [Cu(POP)+(6-CF3bpy)][PF6], [Cu(xantphos)(6-CF3bpy)][PF6], or [Cu(xantphos){6,6?-Me2-4,4?-(CF3)2bpy}][PF6] emit yellow electroluminescence. The LEC with [Cu(xantphos){6,6?-Me2-4,4?-(CF3)2bpy}][PF6] had the fastest turn-on time (8 min), and the LEC with the longest lifetime (t1/2=31 h) contained [Cu(xantphos)(6-CF3bpy)][PF6]; these LECs reached maximum luminances of 131 and 109 cd m?2, 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

Can You Really Do Chemisty Experiments About (9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine)

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The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.161265-03-8, Name is (9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine), molecular formula is C39H32OP2. In a Article,once mentioned of 161265-03-8, category: chiral-phosphine-ligands

The unique amphiphilic Zwitterionic P,O-hybrid ligand (L1) containing phosphino-fragment and ?SO3? group was synthesized and firstly applied in Au-catalyzed hydration of alkynes. Without the aid of any auxiliary additive such as acid or silver salt, L1-based Au-catalyst exhibited excellent activity towards hydration of alkynes to yield ketones with 100% selectivity according to Markovnikov’s rule. On the other hand, L1-based Au-catalyst could be recycled for 4 runs in room temperature ionic liquid of [Bmim]PF6 without obvious activity loss, and also exhibited wide generality to the hydration of different alkynes.

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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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166330-10-5, Name is (Oxybis(2,1-phenylene))bis(diphenylphosphine), molecular formula is C36H28OP2, belongs to chiral-phosphine-ligands compound, is a common compound. In a patnet, once mentioned the new application about 166330-10-5, Computed Properties of C36H28OP2

The new rhenium complexes, [ReOCl3(L2)], incorporating bidentate organophosphorus ligands [L2 = dppe-F 20 (the perfluorinated analog of dppe), xantphos, rac-BINAP, biphep and DPEphos] were successfully synthesized using [ReOCl3(AsPh 3)2] as the precursor. The complexes were characterized by 1R, 1H and 31P NMR, elemental analysis and X-ray diffraction, The X-ray structures reveal a distorted octahedral geometry with a facial arrangement of chloro ligands and an axial rhenium-oxo group. The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2005.

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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 provides compounds of Formula (I), or a pharmaceutically acceptable salt thereof, where R1, R2, R3, R4, R5, R6, A and n are as defined herein. A deuteriated derivative of the compound of Formula (I) is also provided.

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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 reaction mechanisms of Rh-catalyzed regioselective hydrothiolation of the allyl amine employing four bidentate phosphine ligands are investigated with DFT calculations. The free energy profiles of anti-Markovnikov and Markovnikov pathways arising from different alkene insertion types are computed to elucidate the ligand-controlled regioselectivity. For 1,2-bis(diphenylphosphino)benzene (dppbz) and 1,3-bis(diphenylphosphino)propane (dppp) ligands with small nature bite angle (betan ? 86), the anti-Markovnikov pathway that features the 1,2-alkene insertion into Rh-H bond is favored by 2 ? 4 kcal/mol in barriers of elementary steps. While for 1,4-bis(diphenylphosphino)butane (dppb) and bis(2-diphenylphosphinophenyl)ether (DPEphos) ligands with large nature bite angle (betan ? 99), the Markovnikov pathway with 1,2-alkene insertion into Rh-S bond is preferential by 2 ? 7 kcal/mol in barriers. The P-Rh-P bite angle is a reliable predictor and regulator of the regioselectivity of reaction as evidenced by good correlations between reaction barrier and P-Rh-P bite angle. Smaller P-Rh-P bite angle in TSs is generally found for small nature bite angle ligand dppbz and dppp in preferential anti-Markovnikov pathway, while TSs with larger P-Rh-P bite angle are favored by large nature bite angle ligand DPEphos and dppb. Larger difference in P-Rh-P bite angles of TSs between Markovnikov and anti-Markovnikov pathway generally leads to the greater disparity in barrier heights of two pathways, and hence greater regiodivergency of reaction.

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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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Heteroleptic neutral mononuclear cuprous complexes with dipyrrin derivatives and phosphine mixed-ligands including 1,3,7,9-tetramethyldipyrrin (1), 5-phenyl-1,3,7,9-tetramethyldipyrrin (2), 2,8-dibromo-1,3,7,9- tetramethyldipyrrin (3), 1,9-dichloro-5-phenyldipyrrin (4), 1,9-dibromo-5- phenyldipyrrin (5), 5-pentafluorophenyl-1,3,7,9-tetramethyldipyrrin (6) and 1,5,9-triphenyldipyrrin (7) have been synthesized and fully characterized. The central Cu(i) atoms of these complexes in general formulas of Cu(1-6)(PPh 3)2 (1a-6a) and Cu(1-6)(DPEphos) (1b-6b) [DPEphos = bis(2-diphenylphosphinophenyl)ether] all exhibit a pseudo-tetrahedral geometry, while complex Cu(7)(PPh3) (7a) is tricoordinated in a pyramidal conformation due to the large steric hindrance of ligand 7. The oxidation potentials assigned to oxidations of Cu(i)-Cu(ii) are extraordinarily low in the range of 0.36-1.02 V vs. Ag/AgCl compared with traditional [Cu(phen)(PP)] + analogues. Their emission maxima range from 495 to 595 nm in dichloromethane at room temperature with quantum yields of 0.05-4.03% and lifetimes on the order of nanoseconds. Unlike the characteristic MLCT emission in cationic Cu(i) complexes, the emissions are assigned to the dipyrrin-centered intraligand charge transition (ILCT) based on the fact that the increased conjugation within the dipyrrinato anion leads to a weaker metal-ligand interaction, thus preventing the mixing of pi orbitals of ligand and 3d orbitals of Cu(i) atom. This conclusion is also supported by electrochemical data and theoretical 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

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Homogeneous palladium-catalyzed (Pd-catalyzed) cyclocarbonylation of unsaturated allylic alcohols and alkynols in the presence of hydrogen forms lactone products with important applications in the food, perfume, and polymer industry. In this work, the cyclocarbonylation of 2-methyl-3-buten-2-ol was studied for the first time using a very active Pd-DPEphos (bis[(2-diphenylphosphino)phenyl]ether) catalyst in the presence of the ionic liquid (IL) [BMIM]Cl (1-butyl-3-methylimidazolium chloride) in dichloromethane to selectively produce 4,4-dimethyl–butyrolactone. The effect of different parameters such as temperature, gas partial pressures, time of reaction, substrate and ligand concentrations were investigated and found to provide optimal conditions for lactonization (95 C, 28 bar (CO/H2/N2: 20/5/3)), 18 h, 0.1 M substrate, and 16 mol% DPEphos), which were significantly milder than previously reported systems for cyclocarbonylation. Importantly, the study further showed that presence of the IL in the reaction mixture provided stabilization of the catalyst system and prevented formation of Pd-black, which allowed reuse of the catalytic system in consecutive reactions after intermediate extraction of the lactone product.

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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 syntheses and characterization of series of new metallocene-bridged diphosphines and the structures of complexes of some of them with Pd(II) are reported. These complexes were examined as the catalysts in amination reactions of halogenoarenes and in the Suzuki reaction. The complexes based on ruthenocene (2) and osmocene (3) showed lower activities then the palladium complex with dppf in amination reactions and the same activities in the Suzuki reaction. New palladium complexes with the bidentate bulky and electron-rich ligands Fe(eta5-C5H4P(o-PriC 6H4)2)2 (6) and Feeta5- C5H4P(o-MeOC6H4)2) 2 (5) showed a very high catalytic activity in amination and Suzuki coupling of aryl bromides. A complex with ligand 6 was used in the amination of 4-bromotoluene by primary and secondary amines and showed excellent activity.

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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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Transition-metal-catalyzed C-alkylation of ketones and secondary alcohols, with alcohols, avoids use of organometallic or environmentally unfriendly alkylating agents by means of borrowing hydrogen (BH) or hydrogen autotransfer (HA) activation of the alcohol substrates. Water is formed as the only by-product, thus making the BH process atom-economical and environmentally benign. Diverse homogeneous and heterogeneous transition-metal catalysts, ketones, and alcohols can be used for this transformation, thus rendering the BH process promising for replacing those procedures that use traditional alkylating agents. This Minireview summarizes the advances during the last five years in transition-metal-catalyzed BH alpha-alkylation of ketones, and beta-alkylation of secondary alcohols with alcohols. A discussion on the application of the BH strategy for C-C bond formation is included. Something borrowed: The major advances during the past five years in transition-metal-catalyzed borrowing-hydrogen (BH) alkylation of ketones, secondary alcohols, and related compounds with alcohols are summarized. Water is formed as the only by-product, thus making the BH process atom-economical and environmentally benign.

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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