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Reaction of 1,2-bis(diphenylphosphino)benzene (dppbz) with [{Ru(CO)2Cl2}n] affords [Ru(dppbz)(CO)2Cl2], where the two carbonyls are mutually cis and the two chlorides are trans. The molecular structure of [Ru(dppbz)(CO)2Cl2], has been determined by X-ray crystallography, and the stability of the different available stereoisomers has been computationally evaluated. [Ru(dppbz)(CO)2Cl2] has been found to serve as an excellent pre-catalyst for catalytic Suzuki-type C-C coupling and Buchwald-type C-N coupling reactions.

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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 rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.13991-08-7, Name is 1,2-Bis(diphenylphosphino)benzene, molecular formula is C30H24P2. In a Patent,once mentioned of 13991-08-7, Formula: C30H24P2

The alpha,beta-unsaturated ketone moiety of a substrate representative of non-food based biomass was hydrogenated to the corresponding saturated alcohol moiety using a composition including (1) a copper salt; (2) a phosphine; (3) a polar aprotic solvent such as acetonitrile, and (4) a compound suitable for providing hydrogen for the hydrogenation, such as a suitable silane material or a suitable siloxane material.

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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 complex derived from Pd2(dba)3 and dppp catalyzes the addition reaction of aroyl/heteroaroyl acid anhydrides to norbornenes, giving 2-aroyl/heteroaroyl-3-aroyloxy/heteroaroyloxy-bicyclo[2,2,1]heptanes. The C-O bond of acid anhydride is cleaved, and the aroyl/heteroaroyl and aroyloxy/heteroaroyloxy groups are added to alkenes. trans-Adducts are selectively obtained with the endo-benzoyl group and exo-benzoyloxy 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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Heating the 50-electron cluster [Fe3(CO)9 (mu3-Te)2] (1) with the diphosphines Ph2P-R-PPh2 [R = -CH2CH2- (dppe), Z-CH=CH- (dppv), 1,2-C6H4 (dppb), -CH2CH2CH2- (dpp), ferrocenyl (dppf), naphthalenyl (dppbn)] in benzene affords the 52-electron diphosphine-containing tellurium-capped triiron clusters [Fe3(CO)8 (mu3-Te)2 (kappa2-diphosphine)] (diphosphine = dppe, dppv, dppb, dpp, dppf, dppnd) (2?7) in moderate yields, resulting from both phosphine addition and carbonyl loss. With 1,2-bis(diphenylphosphino)benzene (dppb) a second product is the cubane cluster [Fe4(CO)10(mu3-Te)4 (kappa2-dppb)] (8). Cyclic voltammetry measurements on 2?7 reveal that all clusters show irreversible reductive behaviour at ca. ?1.85 V with a series of associated small back oxidation waves, suggesting that reduction leads to significant structural change but that this can be reversed chemically. Oxidation occurs at relatively low potentials and is diphosphine-dependent. The first oxidation appears at ca. +0.35 V for 2?6 with a small degree of reversibility but is as low as +0.14 V for the bis(diphenylphosphino)naphthalene derivative 7 and in some cases is followed by further closely-spaced oxidation. Addition of [Cp2Fe][PF6] to 2?7 results in the formation of new clusters formulated as [Fe3(CO)8(mu3-Te)2(kappa2-diphosphine)]+, with their IR spectra suggesting oxidation at the diiron centre. This is supported by computational studies (DFT) of the bis(diphenylphosphino)propane cluster 5 showing that the HOMO is the Fe?Fe sigma-bonding orbital, while the LUMO is centered on the diphosphine-substituted iron atom and has significant Fe?Te sigma?-anti-bonding character consistent with the irreversible nature of the reduction. Complexes 2?7 have been examined as proton reduction catalysts in the presence of para-toluenesulfonic acid (TsOH). All are active at their first reduction potential, with a second catalytic process being observed at slightly higher potentials. While their overall electrocatalytic behaviour is similar to that noted for [Fe2(CO)6{mu-E(CH2)3E}] (E = S, Se, Te), the DFT results suggest that as the added electron is localised on the unique iron atom. The mechanistic aspects of hydrogen formation are likely to be quite different from the more widely studied diiron models.

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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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This review summarizes the syntheses and reactivities of Groups 6, 7, and 8 metal nitrido and imido complexes reported until August 2002. We begin with a general description of the bonding and reactivity of transition metal nitrido and imido complexes followed by a discussion of the common synthetic routes. The main focus of the review is the survey of the nitrido and imido complexes of Groups 6-8 with an emphasis on their synthesis and reactivity.

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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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This communication describes the synthesis of a series of diphosphine NiII(Ph)(CF3) complexes and studies of their reactivity toward oxidatively induced Ph-CF3 bond-forming reductive elimination. Treatment of these complexes with the one-electron outer-sphere oxidant ferrocenium hexafluorophosphate (FcPF6) affords benzotrifluoride, but the yield varies dramatically as a function of diphosphine ligand. Diphosphines with bite angles of less than 92 afforded <10% yield of PhCF3. In contrast, those with bite angles between 95 and 102 formed PhCF3 in yields ranging from 62 to 77%. If you are hungry for even more, make sure to check my other article about 13991-08-7. Reference of 13991-08-7

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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N-formylation of a wide range of amines proceeded using copper-diphosphine complexes as homogeneous catalysts with polymethylhydrosiloxane (PMHS) under 1 atm of CO2. In the reaction of piperidine, for example, the turnover number (TON) reached 11700 in 23 h with 90% yield of the formylated product. This TON value is much higher than those of the reported catalysts for the formylation of amines under 1 atm of CO2 with hydrosilanes. The Cu complexes with phosphines having ortho-phenylene structures acted as good ligands for the formylation, as compared to a bidentate ligand connected with a propyl chain and a monodentate ligand. Among these diphosphines, ligands with alkyl functionalities, such as isopropyl and cyclohexyl groups, produced better results than the phenyl group. Not only cyclic secondary amines, but also linear secondary amines and aromatic and aliphatic primary amines were found to be reactive substrates. In the case of 2,2,6,6-tetramethylpiperidin-4-amine, the formylation proceeded regioselectively. A catalytic reaction pathway was proposed from a separate experiment using [Me2NCO2] [Me2NH2]. The Royal Society of Chemistry 2013.

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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 straightforward methodology for the synthesis of libraries of chiral tris-ligated cationic platinum complexes and their in situ evaluation as asymmetric carbophilic catalysts in a model domino hydroarylation/cyclization reaction of a 1,6-enyne was developed. A catalyst-generation process based on a combination of a monodentate and a bidentate phosphorus ligand allowed the formation of 108 chiral complexes. One-pot screening of the stereoinduction obtained with this library in a test domino addition/cyclization reaction validated this approach and stressed the key role played by the monodentate ligand partner in obtaining high enantioselectivities. In the case of two challenging substrate/nucleophile combinations, the combinatorial approach resulted in a significant gain in enantioselectivity.

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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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Chelation kinetics of the complexes Ru(CO)4(eta1-(P-P)) have been studied in heptane, where P-P = Ph2P(CH2)nPPh2 (n = 1, 2, 3, or 4, i.e., dppm, dppe, dppp, or dppb), Ph2P(NMe)PPh2 (dppma), Ph2P(o-C6H4)PPh2 (dpp-benzene), or R2P(CH2)2PR2 (R = Me or Cy, i.e., dmpe or dcpe). The complexes were prepared in situ by reaction of the bidentate ligands with Ru(CO)4(C2H4), which itself was prepared in situ by photolysis of Ru3(CO)12 under C2H4. The initially formed Ru(CO)4(eta1-(P-P)) complexes react cleanly to form axial-equatorial Ru(CO)3(eta2-(P-P)), as shown by the crystallographic structures of the products when P-P = dppe, dmpe, and dpp-benzene and the close similarity of their FTIR spectra to those of the other products. The chelated products undergo further reaction in solution or the solid state, and the product when P-P = dppma has been characterized by crystallography as Ru2-(CO)3(mu-PPh2)(mu-Ph2PNMePPh2). The kinetics of the displacement of CO from Ru(CO)4(eta1-(P-P)) in n-heptane are characterized by DeltaH? values that are lower by up to 9 kcal mol-1 than those of their monodentate P-donor analogues. DeltaS? values range from quite positive to slightly negative and suggest a trend from purely dissociative to appreciably associative mechanisms along the series P-P = dpp-benzene < dcpe < dmpe < dppp ? dppm ? dppbu ? dppe ? dppma. This contrasts with the CO-dissociative reactions of analogous Ru(CO)4L complexes when L = monodentate P-donor ligands. If you are hungry for even more, make sure to check my other article about 13991-08-7. Electric Literature of 13991-08-7

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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Catalyst composition produced by combining a cobalt-containing precursor in an alkyl alcohol with a phosphine ligand to the solution; and subsequently adding an iodine compound. Reductive carbonylation processes using the catalyst composition to produce aldehydes are 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