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A series of copper(I) complexes bearing a bis(diphenylphosphoryl)amide (dppaO2?) ligand and a diphosphine ligand were synthesized, and their photophysical properties were investigated. Two complexes, [Cu(dppaO2)(DPEphos)] {DPEphos = bis[2-(diphenylphosphanyl)phenyl] ether} and [Cu(dppaO2)(XANTPHOS)] [XANTPHOS = 9,9-dimethyl-4,5-bis(diphenylphosphanyl)xanthene], show bright white-blue and deep blue luminescence, respectively, in the solid state. The quantum yield of [Cu(dppaO2)(XANTPHOS)] is 0.76 under argon and 0.38 under air. The emission decay curves under argon [tau = 7.9 (17 %), 30.0 mus (83 %)] in the solid state are longer than those under air [tau = 2.5 (19 %), 13.9 mus (81 %)]. The photophysical properties of the complexes are discussed together with the results of DFT and time-dependent DFT (TD-DFT) 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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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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A series of gold(I) iodide complexes 1?11 have been prepared from di-, tri-, and tetraphosphane ligands. Crystallographic studies reveal that the di- (1?7) and tetrametallic (11) compounds feature linearly coordinated gold(I) ions with short aurophilic contacts. Their luminescence behavior is determined by the combined influence of the phosphane properties, metal?metal interaction, and intermolecular lattice-defined interactions. The proposed variable contribution of 3(X+M)-centered (X=halogen; M=metal) and 3XLCT (halogen to ligand charge transfer) electronic transitions into the lowest lying excited state, which is influenced by supramolecular packing, is presumably responsible for the alteration of room-temperature emission color from green (lambda=545 nm, for 11) to near-IR (lambda=698 nm, for 2). Dinuclear compounds 6 and 7 exhibit distinct luminescence thermochromism with a blueshift up to 5750 cm?1 upon cooling. Such dramatic change of emission energy is assigned to the presence of two coupled triplet excited states of 3pipi* and 3(X+M)C/3XLCT nature, the presence of which depends on both molecular structure and the crystal lattice arrangement.

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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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As part of our efforts to identify a suitable back-up compound to our recently disclosed mGlu5 positive allosteric modulator (PAM) clinical candidate VU0490551/JNJ-46778212, this letter details the investigation and challenges of a novel series of 6,7-dihydropyrazolo[1,5-a]pyrazin-4-one derivatives. From these efforts, compound 4k emerged as a potent and selective mGlu5 PAM displaying overall attractive in vitro (pharmacological and ADMET) and PK profiles combined with in vivo efficacy in preclinical models of schizophrenia. However, further advancement of the compound was precluded due to severely limiting CNS-related side-effects confirming the previously reported association between excessive mGlu5 activation and target-related toxicities.

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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 novel tetranuclear Ag(i) complex, [Ag4(mu-DMPTP)2(POP)3][BF4]2 (Ag4N2P3), has been designed to achieve highly efficient thermally activated delayed fluorescence (TADF). Photophysical investigations show that the compound exhibits highly efficient TADF (Phi = 76%) and has a very short ambient-temperature TADF decay time of only 0.65 mus, corresponding to a radiative decay rate of k = Phi/tau = 1.2 × 106 s-1, a value belonging to the fast radiative rates in TADF materials.

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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 dimeric rhodium precursor [Rh(CO)2Cl]2 reacts with two molar equivalent of 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene [xantphos] (a), bis(2-diphenylphosphinophenyl)ether [DPEphos] (b) and their corresponding dioxide analogues xantphos dioxide (c), DPEphos dioxide (d) to afford the mono- and dicarbonyl complexes of the type [Rh(CO)Cl(L)] (1a,1b) and [Rh(CO)2Cl(L)] (1c,1d) respectively, where L = a-d. The complexes 1a-1d have been characterized by elemental analyses, IR and NMR (1H, 31P and 13C) spectroscopy, and the structure of the ligand d was determined by single crystal X-ray diffraction. 1a-1d undergo oxidative addition (OA) reactions with different electrophiles such as CH3I, C2H5I and I2 to give Rh(III) complexes of the types [Rh(CO)y(COR)ClXL] {R = -CH3 (2a-2d), -C2H5 (3a-3d); X = I and y = 0, L = a, b; y = 1, L = c, d} and [Rh(CO)ClI2L] (4a-4d) respectively. Kinetic data for the reactions of 1a-1d with CH3I indicate a pseudo-first-order reaction. The catalytic activity of 1a-1d for the carbonylation of methanol to acetic acid and its ester was evaluated at different CO pressure 15, 20 and 33 bar at 130 C and a higher Turn Over Number (TON) (679-1768) were obtained compared to that of the well-known commercial species [Rh(CO)2I2]- (TON = 463-1000) in each case under the similar experimental conditions.

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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 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

Some scientific research about (9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine)

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The homolytic bond dissociation energies of a series of five- and six-coordinate mono- and dihydride complexes of the type HM(diphosphine)2 and [H2M(diphosphine)2]+ (where M = Co, Rh, and Ir) are calculated and compared with experimental values. This work probes the relationship between the homolytic bond dissociation energies (HMBDEs) of these complexes in these two different coordination environments and formal oxidation states. The results of these calculations and previous experimental observations suggest that for M = Rh the HMBDE of the five-coordinate HM(diphosphine)2 species are 0-2 kcal/mol larger than the HMBDE of the corresponding six-coordinate [H2M(diphosphine)2]+ species. For M = Ir the bond energies of the five- and six-coordinate complexes are nearly the same and for M = Co the six-coordinate species are 1-5 kcal/mol less than the corresponding five-coordinate species. Simplified models of large and complicated ligands seem to capture the essential trends and give very good estimates of these thermodynamic properties compared with experimentally available data that are difficult to obtain. (Chemical Equation 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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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