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The reaction between 1,1′-bis(diphenylphosphino)ferrocene (dppf) and the tricobalt cluster PhCCo3(CO)9 (1) yields the disubstituted cluster PhCCo3(CO)7(dppf) (2).The dppf ligand in 2 bridges adjacent cobalt centers via axial coordination.Ligand substitution leading to 2 may be achieved by thermolysis, oxidative decarbonylation using trimethylamine oxide, and by electron-transfer chain (ETC) catalysis using sodium benzophenone ketyl.The isolated yield of 2 ranged from 50 to 70percent in all cases.Solution characterization of 2 by FT-IR and 31P NMR spectroscopy is presented along with the single-crystal X-ray diffraction results.The dppf-bridged cluster PhCCo3(CO)7(dppf)*(toluene) crystallized in the monoclinic space group P21/c with a = 13.560(3), b = 17.339(3), c = 21.482(3) Angstroem, beta = 106.81(1) deg, V = 4835(1) Angstroem3 and Z = 4.Block-cascade least-squares refinement yielded R = 0.0630 for 5055 (I > 3?(I)) reflections.The redox reactivity of 2 was examined by cyclic voltammetry, which revealed the presence of two irreversible oxidations that are attributed to the oxidation of the dppf ligand and the cluster core along with the observation of an irreversible reduction that exhibits cyclic voltammetric curve crossing.All of the redox processes are discussed with respect to existing tricobalt cluster redox chemistry.

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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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Discovery of enantioselective catalytic reactions for the preparation of chiral compounds from readily available precursors, using scalable and environmentally benign chemistry, can greatly impact their design, synthesis, and eventually manufacture on scale. Functionalized cyclobutanes and cyclobutenes are important structural motifs seen in many bioactive natural products and pharmaceutically relevant small molecules. They are also useful precursors for other classes of organic compounds such as other cycloalkane derivatives, heterocyclic compounds, stereodefined 1,3-dienes, and ligands for catalytic asymmetric synthesis. The simplest approach to make cyclobutenes is through an enantioselective [2 + 2]-cycloaddition between an alkyne and an alkenyl derivative, a reaction which has a long history. Yet known reactions of this class that give acceptable enantioselectivities are of very narrow scope and are strictly limited to activated alkynes and highly reactive alkenes. Here, we disclose a broadly applicable enantioselective [2 + 2]-cycloaddition between wide variety of alkynes and alkenyl derivatives, two of the most abundant classes of organic precursors. The key cycloaddition reaction employs catalysts derived from readily synthesized ligands and an earth-abundant metal, cobalt. Over 50 different cyclobutenes with enantioselectivities in the range of 86-97% ee are documented. With the diverse functional groups present in these compounds, further diastereoselective transformations are easily envisaged for synthesis of highly functionalized cyclobutanes and cyclobutenes. Some of the novel observations made during these studies including a key role of a cationic Co(I)-intermediate, ligand and counterion effects on the reactions, can be expected to have broad implications in homogeneous catalysis beyond the highly valuable synthetic intermediates that are accessible by this route.

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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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Reaction of 1-naphthylamine with ethyl benzoylacetate gives the corresponding benzoyl acetamide derivative 1, which undergoes cyclization to 4-phenylbenzo[h]quinolin-2(1H)-one (2) in the presence of H2SO4. Bromination with POBr3, followed by reaction with n-BuLi and DMF, gives 4-phenylbenzo[h]quinoline-2-carbaldehyde (4), which is converted to the corresponding oxime hydrochloride 5 with NH2OH·HCl. Hydrogenation of 5 catalyzed by 10% Pd/C (type 338) leads to 4-phenyl-2-aminomethylbenzo[h]quinoline hydrochloride (HCNNPh·HCl, 6) isolated in high yield. Similarly, the 4-methyl-2-aminomethylbenzo[h]quinoline derivative (HCNNMe·HCl, 12) is prepared starting from 1-naphthylamine and 2,2,6-trimethyl-4H-1,3-dioxin-4-one, following the route for 6. Reaction of RuCl2(PPh3)3 with a diphosphine (PP), the HCl salt 6, and NEt3 in 2-propanol leads to the pincer complexes RuCl(CNNPh)(PP) (PP = Ph2P(CH2)3PPh2, 13; Ph2P(CH2)4PPh2, 14; 1,1?-bis(diphenylphosphino)ferrocene, 15). The methyl derivatives RuCl(CNNMe)(PP) (PP = Ph2P(CH2)3PPh2, 16; Ph2P(CH2)4PPh2, 17; 1,1?-bis(diphenylphosphino)ferrocene, 18) are obtained in a similar way using 12 in place of 6. Treatment of [RuCl2(p-cymene)]2 with rac-BINAP, 6, and NEt3 affords RuCl(CNNPh)(BINAP) (19), isolated as a mixture of two diastereoisomers (3:4 molar ratio). The chiral RuCl(CNNPh)[(S,R)-JOSIPHOS] (20) is obtained as a single isomer from [RuCl2(p-cymene)]2, (S,R)-JOSIPHOS, and 6. Complexes 13-20 efficiently catalyze the transfer hydrogenation of acetophenone in 2-propanol at reflux in the presence of NaOiPr (2 mol%) with S/C = 5000-20-000 and at high rate (TOF up to 6.7 × 103 min-1). With complexes 13, 15, 17, and 18 several ketones of commercial-grade purity have been reduced to alcohols, including the bulky RCO(tBu) (R = Me, Ph) substrates. With 20 acetophenone is reduced to (S)-1-phenylethanol with 85% ee. The pincer complexes 13-15 and 18 are also found highly active in the hydrogenation of ketones at 40 C with an S/C = 10-000, under 5 bar of dihydrogen in methanol and in the presence of 2 mol % of a base (NaOH, KOH, NaOMe).

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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 range of ruthenium-arene compounds with chloride, bromide or iodide ligands were prepared and tested as catalysts for the homogeneous redox neutral alkylation of tert-butylamine with phenethyl alcohol, and compared to the previously reported catalyst [RuCl2(p-cymene)]2, in the presence of the diphosphine 1,1?-bis(diphenylphosphino)ferrocene (dppf). The best catalytic activities were obtained with ruthenium iodide compounds. The formation of either [RuX(p-cymene)(dppf)][X] or [(RuX2(p-cymene))2(dppf)] (X = halide) under the catalytic conditions employed was investigated. Haloruthenium arene complexes have been tested as catalysts for the homogeneous redox neutral alkylation of tert-butylamine with phenethyl alcohol in the presence of 1,1?-bis(diphenylphosphino)ferrocene (dppf). Halide identity and arene substitutions influence the catalytic activity and both RuX(p-cymene)(dppf)][X] and [(RuX2(p-cymene))2(dppf)] (X = halide) appear to play a role in catalysis.

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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 invention discloses a method for preparing ferrocene diphosphine ligand, and belongs to the field of organic synthesis. The method comprises the following steps: by taking ferrocene as an initial raw material and boron trifluoride diethyl etherate as a catalyst, reacting with diaryl phosphine oxide or dialkyl phosphine oxide, hydrolyzing so as to obtain tertfluoborate of a ferrocene diphosphine compound, and performing heating backflow deprotection in methanol, thereby obtaining the ferrocene diphosphine compound. Compared with the prior art, the method is gentle in reaction condition, simple in aftertreatment, and relatively applicable to industrial production, and the yield is greater than 90%. The prepared ferrocene diphosphine can be used as ligand of a metal catalyst, and can be used in the fields such as organic optoelectronic materials and medicines.

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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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Fe(C5H4PPh2)2 (dppf) undergoes facile thermal substitution reactions with R2C2Co2(CO)6 (R = MeO2C, CF3) to yield a variety of products. When R = MeO2C, initial coordination gives mu2-(MeO2C)2C2Co2(CO)5(eta;1-dppf); its crystal and molecular structure, monoclinic, P21/c, a = 8.954(3), b = 20.211(2) c = 23.836(5) A, beta = 100.55(2), Z = 4, R1 = 0.0345 for 5764 reflections 1 > 2 sigma (I), confirms the monodentate coordination mode for dppf. At low dppf/alkyne-complex ratios, oligomeric products with dppf ligands linking up to five (mu2-MeO2C)2C2Co2 modules have been characterised but, as the proportion of the phosphine ligand increases, unstable products, which include a eta1-mu-eta1 dppf configuration, are obtained as well. In contrast, for R = CF3, only [(CF3)2C2]Co2(CO)4(eta2-dppf) is found in significant yield. A molecule with two different reduction centres, [mu2-(MeO2C)2C2Co2(CO)5](mu-dppf)[Co3(mu3-CPh)(CO)8], was also characterised. Electrochemistry of the dppf complexes was characterised by fast ligand dissociation upon reduction of the (mu-alkyne)Co2 redox centre and oxidation of coordinated dppf. There was no evidence for communication between redox centres.

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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 synthesis of diverse ferrocenyl phosphane nickel carbonyls of type (FcPPh2)Ni(CO)3 (3), (FcPPh2)2Ni(CO)2 (4), fc(PR2Ni(CO)3)2 (R = Ph (6a), R = p-tolyl (6b)), and (fc(PPh2)2)Ni(CO)2 (7) (Fc = (eta5-C5H5)(eta5-C5H4)Fe, fc = (eta5-C5H4)2Fe) starting from FcPPh2 (1), fc(PR2)2 (R = Ph (5a); R = p-tolyl (5b)), and Ni(CO)4 (2) is described. The structures of 3, 4, 6b, and 7 in the solid state are reported, intermolecular interactions by pi-pi-contacts are discussed. The behavior of 3, 4, 6a, 6b, and 7 towards the oligomerization of ethylene is reported. All compounds, except 4, were found to be inactive in homogeneous ethylene oligomerization, while they exhibit moderate activities (up to 660 kg prod/mol Ni h) in heterogeneous ethylene oligomerization experiments.

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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 interested in 12150-46-8, you can contact me at any time and look forward to more communication.Related Products of 12150-46-8

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 octa-substituted iridium carbonyl derivative [H4Ir4(CO)4{Fe(C5H 3PPh2)(C5H4P(Ph)C6H 4)}2] prepared from [Ir4(CO)12] and dppf consists of a tetrahedral Ir4 unit and two tetradentate dehydrogenated dppf ligands formed upon ortho-metallation of a cyclopentadienyl and a phenyl ring with each iridium atom coordinated by a carbonyl group, a phosphorus and an ortho-carbon of the dehydrogenated cyclopentadienyl or phenyl 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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Reaction of the complexes (R=Me or Ph) either with 2 equivalents of L > or 1 equivalent of L2 for R=Me only> in CH2Cl2 at room temperature affords good yields of the compounds (1)-(24) by successive substitutions of acetonitrile and an alkyne ligand.X-Ray crystallographic studies were carried out on the complex Ph2P(CH2)PPh2(eta2-MeC2Me)> (19).Crystals of (19) are monoclinic, space group P21/n with a=12.208(4), b=13.395(2), c=20.820(6) Angstroem, and beta=104.31(2) deg.The structure was refined to R=0.052 (R’=0.060) for 2860 reflections with F0>3?(F0).The tungsten co-ordination may be described in terms of a pseudo-octahedral structure.The bidentate phosphine ligand, but-2-yne, and an iodide ligand occupy the four equatorial sites, and the carbonyl and iodide ligands the two axial sites.The but-2-yne ligand is oriented so that it is approximately coplanar with the axial ligands.Phosphorus-31 n.m.r. and i.r.spectral studies are interpreted to suggest the likely structures for the other complexes.The barrier to but-2-yne rotation of a number of complexes has been determined by variable-temperature 1H n.m.r. spectroscopy.These results are discussed in terms of the electronic and steric effects of the phosphorus-donor ligands and also the di-iodo complexes are compared with the analogous dibromo and dichloro complexes reported by other workers.The 13C n.m.r. chemical shifts of the alkyne contact carbons suggest that the alkyne ligand is acting as a four-electron donor in these complexes.

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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