161265-03-8| Page 29 of 30 | Chiral phosphine ligands

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Balanced chemical reaction does not necessarily reveal either the individual elementary reactions by which a reaction occurs or its rate law.COA of Formula: C39H32OP2. In my other articles, you can also check out more blogs about 161265-03-8

A catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes, but it must appear in at least one of the elementary reactions in the mechanism for the catalyzed reaction. 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, COA of Formula: C39H32OP2

1,10-Phenanthroline Carboxylic Acids for Preparation of Functionalized Metal-Organic Frameworks

Synthetic approaches to 1,10-phenanthroline-3-carboxylic acid (2), 1,10-phenanthroline-3,8-dicarboxylic acid (3) and their functionalized derivatives were investigated. Acids 2 and 3 were prepared in good yields from bromophenanthrolines via palladium-catalyzed alkoxycarbonylation. Moreover, butyl 8-bromo-1,10-phenanthroline-3-carboxylate was obtained in acceptable yield (25?35%) by ceasing the carbonylation of the dibromide 5 after 30?70% consumption of the starting compound. To prepare functionalized derivatives of acids 2 and 3, the reactions of butyl 8-bromo-1,10-phenanthroline-3-carboxylate and diethyl 4,7-dichloro-1,10-phenanthroline-3,8-dicarboxylate with various nucleophiles were investigated. SNAr reactions are suitable for the synthesis of 4,7-diazido-, dimethoxy- and diamino-substituted 3,8-bis(ethoxycarbonyl)phenanthrolines, including the macrocyclic derivatives. The bromine atom at position 8 of the phenanthroline ring reacts with nucleophiles only in the presence of the palladium catalysts. The scope of these reactions was briefly investigated conducting Sonogashira, Suzuki-Miyaura and Hirao reactions. Hydrolysis of the functionalized esters of phenanthroline leads to corresponding acids in good yields.

Reference£º
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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161265-03-8, Name is (9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine), molecular formula is C39H32OP2, belongs to chiral-phosphine-ligands compound, is a common compound. In a patnet, once mentioned the new application about 161265-03-8, Recommanded Product: (9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine)

Electronic and bite angle effects in catalytic C-O bond cleavage of a lignin model compound using ruthenium Xantphos complexes

Bite angle and electronic effects on the ruthenium-diphosphine catalysed ether bond cleavage of the lignin beta-O-4 model compound 2-phenoxy-1-phenylethanol were tested. Enhanced conversion of the substrate was observed with increasing sigma-donor capacity of the ligands. Kinetic and thermodynamic data suggest oxidative addition of the dehydrogenated model compound to the diphosphine Ru(0) complex to be rate-limiting.

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Balanced chemical reaction does not necessarily reveal either the individual elementary reactions by which a reaction occurs or its rate law.category: chiral-phosphine-ligands. In my other articles, you can also check out more blogs about 161265-03-8

Dual Chalcogen-Chalcogen Bonding Catalysis

The noncovalent S¡¤¡¤¡¤O bonding interaction is an evolutionary force that has been smartly exploited by nature to modulate the conformational preferences of proteins. The employment of this type of weak noncovalent force to drive chemical reactions is promising yet remains largely elusive. Herein, we describe a dual chalcogen-chalcogen bonding catalysis strategy that the distinct chalcogen atoms simultaneously interact with two chalcogen-based electron donors to give rise to the catalytic activity, thus facilitating chemical reactions. Conventional approaches to the Rauhut-Currier-type reactions require the use of strongly nucleophilic Lewis bases as essential promoters. The implementation of this dual chalcogen-chalcogen bonding catalysis strategy allows the simultaneous Se¡¤¡¤¡¤O bonding interaction between chalcogen-bonding donors and an enone and an alcohol, enabling the realization of the Rauhut-Currier-type reactions in a distinct way. The further implementation of a consecutive dual Se¡¤¡¤¡¤O bonding catalysis approach enables the achievement of an initial Rauhut-Currier-type reaction to give an enone product which further undergoes an alcohol-addition induced cyclization reaction. This work demonstrates that the nearly linear chalcogen-bonding interaction can differentiate similar alkyl groups to give rise to regioselectivity. Moreover, the new strategy shows its advantage as it not only enables less reactive substrates working efficiently but tolerates inaccessible substrates using conventional methods.

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Shine bright or live long: Substituent effects in [Cu(N^N)(P^P)]+-based light-emitting electrochemical cells where N^N is a 6-substituted 2,2?-bipyridine

We report [Cu(P^P)(N^N)][PF6] complexes with P^P = bis(2-(diphenylphosphino)phenyl)ether (POP) or 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (xantphos) and N^N = 6-methyl-2,2?-bipyridine (Mebpy), 6-ethyl-2,2?-bipyridine (Etbpy), 6,6?-dimethyl-2,2?-bipyridine (Me2bpy) or 6-phenyl-2,2?-bipyridine (Phbpy). The crystal structures of [Cu(POP)(Phbpy)][PF6]¡¤Et2O, [Cu(POP)(Etbpy)][PF6]¡¤Et2O, [Cu(xantphos)(Me2bpy)][PF6], [Cu(xantphos)(Mebpy)][PF6]¡¤CH2Cl2¡¤0.4Et2O, [Cu(xantphos)(Etbpy)][PF6]¡¤CH2Cl2¡¤1.5H2O and [Cu(xantphos)(Phbpy)][PF6] are described; each copper(i) centre is distorted tetrahedral. In the crystallographically determined structures, the N^N domain in [Cu(xantphos)(Phbpy)]+ and [Cu(POP)(Phbpy)]+ is rotated ?180 with respect to its orientation in [Cu(xantphos)(Mebpy)]+, [Cu(POP)(Etbpy)]+ and [Cu(xantphos)(Etbpy)]+; in each complex containing xantphos, the xanthene ‘bowl’ retains the same conformation in the solid-state structures. The two conformers resulting from the 180 rotation of the N^N ligand were optimized at the B3LYP-D3/(6-31G??+LANL2DZ) level and are close in energy for each complex. Variable temperature NMR spectroscopy evidences the presence of two conformers of [Cu(xantphos)(Phbpy)]+ in solution which are related by inversion of the xanthene unit. The complexes exhibit MLCT absorption bands in the range 378 to 388 nm, and excitation into each MLCT band leads to yellow emissions. Photoluminescence quantum yields (PLQYs) increase from solution to thin-film and powder; the highest PLQYs are observed for powdered [Cu(xantphos)(Mebpy)][PF6] (34%), [Cu(xantphos)(Etbpy)][PF6] (37%) and [Cu(xantphos)(Me2bpy)][PF6] (37%) with lifetimes of 9.6-11 mus. Density functional theory calculations predict that the emitting triplet (T1) involves an electron transfer from the Cu-P^P environment to the N^N ligand and therefore shows a 3MLCT character. T1 is calculated to be ?0.20 eV lower in energy than the first singlet excited state (S1). The [Cu(P^P)(N^N)][PF6] ionic transition-metal (iTMC) complexes were tested in light-emitting electrochemical cells (LECs). Turn-on times are fast, and the LEC with [Cu(xantphos)(Me2bpy)][PF6] achieves a maximum efficacy of 3.0 cd A-1 (luminance = 145 cd m-2) with a lifetime of 1 h; on going to the [Cu(xantphos)(Mebpy)][PF6]-based LEC, the lifetime exceeds 15 h but at the expense of the efficacy (1.9 cd A-1). The lifetimes of LECs containing [Cu(xantphos)(Etbpy)][PF6] and [Cu(POP)(Etbpy)][PF6] exceed 40 and 80 h respectively.

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Metallate Complexes of the Late Transition Metals: Organometallic Chemistry and Catalysis

The synthesis of late transition metallates as well as the role of such species in catalysis is described in this contribution. Their involvement in numerous transition metal-mediated transformations is more significant than thought and could represent a novel starting point from which catalysis can be launched.

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Synthesis of gold clusters with flexible and rigid diphosphine ligands and the effect of spacer and solvent on the size selectivity

The relationship between ligand rigidity and solvent polarity and the size and dispersity of Au cluster suspensions was investigated. Solutions were prepared which contained 10-3mol/L of Chloro(triphenylphosphine) gold(I) [Au(PPh3)Cl], the same concentration of diphosphine ligand, and 5¡Á10-3mol/L of borane-tert-butylamine (BTBC) as the reducing agent. Diphosphine ligands were used which consisted of phosphorus atoms connected by chains with increasing length and rigidity. Specifically we employed a short flexible chain PPh2(CH2)3PPh2, i.e., 1,3-bis(diphenylphosphino)propane, denoted by L3, a long, flexible chain, PPh2(CH2)6PPh2 i.e., 1,6-bis(diphenylphosphino)hexane denoted by L6, two rigid ligands, 4,5-Bis(diphenylphosphino)-9,9-dimethylxanthene (xantphos) denoted by LAr, and 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (BINAP) denoted by LBn, and a moderately flexible spacer 2,2′-Bis(diphenylphosphino)biphenyl (Biphenyl) denoted by LBp. Materials were dissolved in solvents of increasing polarity; from highest to lowest, methanol, ethanol, propanol, butanol and chloroform were used. Samples were characterized using UV-Visible spectroscopy and electrospray ionization mass spectrometry. We observed the formation of stable monodisperse clusters with the shortest ligand, (L3), independent of solvent. With a longer flexible ligand, (L6), we observed primarily Au8-10 cores depending on the ratio of L6/PPh3. All other ligands yielded polydisperse distributions. These dispersions contained clusters with a nuclearity between 8 and 11, for example [Au10(PPh3)9]3+ in LBn and [Au8(PPh3)7]2+ in LBp, were observed in the initial stages, but they were not stable and precipitated out or plated the glass vial. We also observed that the polarity of the solvent did not play a significant role in the formation of MPC’s, however a correlation between the size of the solvent and MPC formation was observed. Selectivity was observed in the smallest solvents, methanol and chloroform, which are the most and least polar solvents, respectively.

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Regiospecific N-heteroarylation of amidines for full-color-tunable boron difluoride dyes with mechanochromic luminescence

Colors to dye for: Palladium-catalyzed regiospecific N-heteroarylations of amidines with 2-halo-N-heteroarenes leads to a structurally diverse library of BF2/amidine-based complexes. These dyes not only present full-visible-color solid-state emissions with large Stokes shifts and high fluorescence quantum yields, but also exhibit a full-color-tunable mechanofluorochromic nature. Copyright

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

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Synthesis and characterization of a large bite angle xantphos iridium complex

The xantphos iridium complex [Ir(xantphos)(H)(CO)(PPh3)] CH 2CL2 (3) was synthesized and structurally characterized by NMR, IR, and single-crystal X-ray diffraction. Complex 3 crystallizes with two molecules (A,B) in the asymmetric unit. The coordination around Ir is trigonal bipyramidal with all three P groups occupying equatorial positions. The carbonyl and hydride occupy axial sites. This mode of bonding results in a complex that exhibited large bite (P1-Ir-P2) angles of 109.12(6) and 110.50(6) for the A and B molecules, respectively. NMR data further support the structural elucidation of 3 and IR data confirm the presence of Ir bound to both a carbonyl and a hydride. Thermal analyses of 3 indicate that it is thermally stable up to >400 C under nitrogen.

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

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Visible-Light-Driven Photosystems Using Heteroleptic Cu(I) Photosensitizers and Rh(III) Catalysts to Produce H2

The synthesis of two new heteroleptic Cu(I) photosensitizers (PS), [Cu(Xantphos)(NN)]PF6 (NN = biq = 2,2?-biquinoline, dmebiq = 2,2?-biquinoline-4,4?-dimethyl ester; Xantphos = 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene), along with the associated structural, photophysical, and electrochemical properties, are described. The biquinoline diimine ligand extends the PS light absorbing properties into the visible with a maximum absorption at 455 and 505 nm for NN = biq and dmebiq, respectively, in CH2Cl2 solvent. Following photoexcitation, both Cu(I) PS are emissive at low energy, albeit displaying stark differences in their excited state lifetimes (MLCT = 410 ¡À 5 (biq) and 44 ¡À 4 ns (dmebiq)). Cyclic voltammetry indicates a Cu-based HOMO and NN-based LUMO for both complexes, whereby the methyl ester substituents stabilize the LUMO within [Cu(Xantphos)(dmebiq)]+ by -0.37 V compared to the unsubstituted analogue. When combined with H2O, N,N-dimethylaniline (DMA) electron donor, and cis-[Rh(NN)2Cl2]PF6 (NN = Me2bpy = 4,4?-dimethyl-2,2?-bipyridine, bpy = 2,2?-bipyridine, dmebpy = 2,2?-bipyridine-4,4?-dimethyl ester) water reduction catalysts (WRC), photocatalytic H2 evolution is only observed using the [Cu(Xantphos)(biq)]+ PS. Furthermore, the choice of cis-[Rh(NN)2Cl2]+ WRC strongly affects the catalytic activity with turnover numbers (TONRh = mol H2 per mol Rh catalyst) of 25 ¡À 3, 22 ¡À 1, and 43 ¡À 3 for NN = Me2bpy, bpy, and dmebpy, respectively. This work illustrates how ligand modification to carefully tune the PS light absorbing, excited state, and redox-active properties, along with the WRC redox potentials, can have a profound impact on the photoinduced intermolecular electron transfer between components and the subsequent catalytic activity.

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D?pi?A Dyes that Contain New Hydantoin Anchoring Groups for Dye-Sensitized Solar Cells

The development of new anchoring groups is important to facilitate effective co-sensitization in dye-sensitized solar cells (DSSCs). Herein, stable organic D?pi?A dyes that contain new heterocyclic hydantoin-based anchoring groups have been designed, synthesized, and used in DSSCs. These dye sensitizers were evaluated in terms of their absorption spectra, electrochemical properties, and performance in DSSC devices. Although only one-third of the amount of hydantoin-containing dyes adsorbed onto TiO2 relative to their cyanoacrylic-acid-containing analogues, they exhibited effective photoexcited electron-transfer properties. External quantum efficiencies of over 80 % was observed, which were comparable to those of the cyanoacrylic-acid-containing dyes. In addition, the new hydantoin-containing dyes exhibited significant robustness, which could allow improved stability of their corresponding photovoltaic devices under harsh conditions, such as high temperature and humidity.

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