Tag: M.W:500-600

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Controlling selectivity in intermolecular alkene or aldehyde hydroacylation reactions catalyzed by {Rh(L2)}+ fragments

Rhodium(III) dihydrido complexes [Rh(L2)(H)2(acetone) ][BArF4] (ArF = C6H 3(CF3)2) containing the potentially hemilabile ligands L2 = 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene (Xantphos) and [Ph2P(CH2)2]2O (POP?) have been prepared from their corresponding norbornadiene rhodium(I) precursors. In solution these complexes are fluxional by proposed acetone dissociation, which can be trapped out by addition of MeCN to form [Rh(L2)(H)2(NCMe)][BArF4], which have been crystallographically characterized. Addition of alkene (methyl acrylate) to these complexes results in reduction to a rhodium(I) species and when followed by addition of the aldehyde HCOCH2CH2SMe affords the new acyl hydrido complexes [Rh(L2)(COCH 2CH2SMe)H][BArF4] in good yield. The solid-state and solution structures show a tight binding of the POP? and Xantphos ligands, having a trans-arrangement of the phosphines with the central ether linkage bound. This is similar to the previously reported complex [Rh(DPEphos)(COCH2CH2SMe)H][BArF4] (DPEphos = [Ph2P(C6H4)]2O). Unlike the DPEphos complex, the Xantphos and POP? ligated complexes are not effective catalysts for the hydroacylation reaction between methyl acrylate and HCOCH2CH2SMe. This is traced to their inability to dissociate the central ether link in a hemilabile manner to reveal a vacant site necessary for alkene coordination. Consistent with this lack of availability of the vacant site, these complexes also are stable toward reductive decarbonylation. Complexes [Rh(Ph2P(CH2) nPPh2)(acetone)2][BArF4] (n = 2-5) have also been studied as catalysts for the hydroacylation reaction between methyl acrylate and HCOCH2CH2SMe at 22 C. As found previously, for n = 2 this affords the product of alkene hydroacylation, but as the chain length is progressively increased to n = 5, the reaction also progressively changes to favor the product of aldehyde hydroacylation. This is suggested to occur by a decrease in the accessibility of the metal site on increasing the bite angle of the chelate ligand, so that alkene coordination to a putative Rh(III)-acyl hydrido intermediate is progressively disfavored and aldehyde coordination (followed by hydride transfer) is progressively favored. These, and previous, results show that the overall conversion in the hydroacylation reaction can be controlled by the hemilabile nature of the chelating phosphine in the catalyst (e.g., DPEphos versus Xantphos), and the course of the reaction can also be tuned by changing the bite angle of the phosphine, cf. Ph2P(CH2)2PPh2 and Ph2P(CH2)5PPh2.

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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

Reference of 166330-10-5. Let¡¯s face it, organic chemistry can seem difficult to learn. Especially from a beginner¡¯s point of view. Like 166330-10-5, Name is (Oxybis(2,1-phenylene))bis(diphenylphosphine). In a document type is Review, introducing its new discovery.

Palladium-Catalyzed Cascade Cyclization/Alkynylation Reactions

Palladium-catalyzed cascade cyclization reactions have witnessed significant improvements in recent years. Among them, palladium-catalyzed cascade cyclization/alkynylation are especially attractive, which can assemble structurally diverse monocyclic, bicyclic, fused polycyclic, and spirocyclic skeletons with excellent chemoselectivities. In this Minireview, palladium-catalyzed cascade cyclization/alkynylation have been summarized and discussed in detail with focus on oxypalladation and aminopalladation-initiated cascade cyclization, intramolecular Heck-type cascade cyclization, carbocyclizations, cascade cyclizations, and other types of cascade cyclization reactions. Some significant and representative synthetic methodologies and their synthetic applications and reaction mechanisms have also been described.

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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

Application of 161265-03-8, Chemistry can be defined as the study of matter and the changes it undergoes. You¡¯ll sometimes hear it called the central science because it is the connection between physics and all the other sciences, starting with biology.161265-03-8, Name is (9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine), molecular formula is C39H32OP2. In a patent, introducing its new discovery.

Remarkable luminescence properties of lanthanide complexes with asymmetric dodecahedron structures

The distorted coordination structures and luminescence properties of novel lanthanide complexes with oxo-linked bidentate phosphane oxide ligands-4,5-bis(diphenylphosphoryl)-9,9-dimethylxanthene (xantpo), 4,5-bis(di-tert-butylphosphoryl)-9,9-dimethylxanthene (tBu-xantpo), and bis[(2-diphenylphosphoryl)phenyl] ether (dpepo)-and low-vibrational frequency hexafluoroacetylacetonato (hfa) ligands are reported. The lanthanide complexes exhibit characteristic square antiprism and trigonal dodecahedron structures with eight-coordinated oxygen atoms. The luminescence properties of these complexes are characterized by their emission quantum yields, emission lifetimes, and their radiative and nonradiative rate constants. Lanthanide complexes with dodecahedron structures offer markedly high emission quantum yields (Eu: 55-72%, Sm: 2.4-5.0% in [D6]acetone) due to enhancement of the electric dipole transition and suppression of vibrational relaxation. These remarkable luminescence properties are elucidated in terms of their distorted coordination structures.

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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

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, Quality Control of: (9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine)

Gold-Catalyzed Oxidative Coupling of Alkynes toward the Synthesis of Cyclic Conjugated Diynes

Gold-catalyzed oxidative coupling of alkynes was developed as an efficient approach for the synthesis of challenging cyclic conjugated diynes (CCD). Compared with the classic copper-promoted oxidative coupling reaction of alkynes, this gold-catalyzed process exhibited a faster reaction rate due to rapid reductive elimination from the Au(III) intermediate. This unique reactivity thus allowed a challenging diyne macrocyclization to take place with high efficiency. Condition screening revealed an [(n-Bu)4N]+[Cl-Au-Cl]? salt as the optimal pre-catalyst. Macrocycles with ring size between 13 and 28 atoms were prepared in moderate to good yields, which highlighted the broad substrate scope of this new strategy. Furthermore, the synthetic utilities of the CCDs for copper-free click chemistry have been demonstrated, showcasing the potential application of this strategy in biological systems. Macrocycles are important structural moieties in medicinal and biological research, and efficient methods for macrocyclization are always in high demand. With the unique conformation having six carbon atoms in a linear geometry, the cyclic conjugated diynes (CCD) present greater synthetic challenges and have been much less explored. Therefore, application of these unique macrocycles in biological studies is largely unexplored. Here, we describe the discovery of gold-catalyzed Glaser-Hay type oxidative coupling of terminal alkynes to achieve CCD under diluted conditions with broad substrate scope and great functional group compatibility. Taking advantage of the 14-member cyclic diyne, a copper-free click chemistry was achieved, which provided an effective alternative strategy for the traditional cyclooctyne-based azide-alkyne cycloaddition, suggesting a promising future for this method in tackling challenging problems in related biological and medicinal research. Gold-catalyzed oxidative coupling of alkynes was developed as an efficient approach for the synthesis of challenging cyclic conjugated diyne. Compared with copper-promoted oxidative coupling, this protocol allowed macrocyclization under dilute conditions with good overall reactivity and high functional group tolerance. The success in achieving copper-free click chemistry on cyclic conjugated diyne highlights its potential application in biological and medicinal research.

Balanced chemical reaction does not necessarily reveal either the individual elementary reactions by which a reaction occurs or its rate law.Quality Control of: (9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine). In my other articles, you can also check out more blogs about 161265-03-8

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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

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. 12150-46-8, Name is 1,1-Bis(diphenylphosphino)ferrocene, molecular formula is C34H28FeP2. In a Article£¬once mentioned of 12150-46-8, SDS of cas: 12150-46-8

Mono- and Di-dentate Tertiary Phosphine and Monodentate Tertiary Phosphite Derivatives of

The reactions of the butterfly cluster with a range of tertiary phosphines and diphosphines and with a large excess of trimethyl phosphite have been explored.Twenty-two derivatives of the general types (x=1 or 2), xBH2> (x=2-4), Ru4H(CO)11(L-L)BH2>, and <2> (L-L=diphosphine) have been synthesised and characterised by mass spectrometry and IR and multinuclear NMR spectroscopies.The single-crystal structures of , trans-2BH2> and *CH2Cl2 (dppe=Ph2PCH2CH2PPh2) have been determined.In the PPh3 ligand occupies a wing-tip equatorial site.In 2BH2> the two P(OMe)3 ligands are also in such sites and both the isomers in which these ligands are mutually cis or trans with respect to the cluster core are formed; the solid-state structure of the trans isomer has been confirmed.When the two phosphorus-donor atoms are provided in the form of a didentate ligand the sites of co-ordination depend upon the nature of the backbone of the ligand.In , the dppe ligand bridges a Rwing tip-Ruhinge edge and two isomers are observed in solution; the solid-state structure of one isomer has been elucidated.Use of the diphosphine ligands allows the formation of linked dicluster species, and the competition for the formation of linked and monocluster species in which the ligand behaves in either a mono- or di-dentate fashion has been investigated.In the case of dppa an additional product when the ligand is in a four-fold excess is in which both dppa ligands are pendant and co-ordinated to different wing-tip ruthenium atoms.

Sometimes chemists are able to propose two or more mechanisms that are consistent with the available data.SDS of cas: 12150-46-8, If a proposed mechanism predicts the wrong experimental rate law, however, the mechanism must be incorrect.Welcome to check out more blogs about 12150-46-8, in my other articles.

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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

The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.12150-46-8, Name is 1,1-Bis(diphenylphosphino)ferrocene, molecular formula is C34H28FeP2. In a Article£¬once mentioned of 12150-46-8, category: chiral-phosphine-ligands

Regioselective c-f bond activation of hexafluoropropylene on palladium(0): Formation of a cationic H2-perfluoroallylpalladium complex

A chemoselective C(sp2) -F or C(sp3)-F bond activation of hexafluoropropylene (HFP) was achieved by adopting the proper combination of a Lewis acid co-additive with a ligand which coordinates Pd0. The treatment of [(h2- HFP)Pd(PCy3)2] with B(C6F5)3 allowed a chemoselective C- (sp3)-F bond cleavage of HFP to give a unique cationic perfluoroallypalladium complex. In this complex, the coordination mode of the perfluoroallyl ligand was considered to be of the unique h2-fashion.

Note that a catalyst decreases the activation energy for both the forward and the reverse reactions and hence accelerates both the forward and the reverse reactions.category: chiral-phosphine-ligands, you can also check out more blogs about12150-46-8

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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

Chemistry is an experimental science, and the best way to enjoy it and learn about it is performing experiments.Introducing a new discovery about 166330-10-5, Name is (Oxybis(2,1-phenylene))bis(diphenylphosphine), Formula: C36H28OP2.

Synthesis of (Z)-1-thio- and (Z)-2-thio-1-alkenyl boronates via copper-catalyzed regiodivergent hydroboration of thioacetylenes: An experimental and theoretical study

A Cu-catalyzed divergent hydroboration of thioacetylenes has been achieved, providing (Z)-1-thio- or (Z)-2-thio-1-alkenyl boronates in moderate to high yields with excellent regio- and stereoselectivity, by using pinacolborane or bis(pinacolato)diboron as the hydroborating reagents, respectively. DFT calculations indicate that the sulfur atom plays a key role in determining the regioselectivity through polarizing the C-C triple bonds and participating in the HOMO orbitals. Moreover, the SR group can serve as a good leaving group, resulting in the concise synthesis of six regio- and stereoisomers of trisubstituted alkenes 5 via the iterative cross-coupling of C-B and C-S bonds. Clearly, it will be valuable for assembling stereochemically diverse trisubstituted olefins in organic synthesis.

Balanced chemical reaction does not necessarily reveal either the individual elementary reactions by which a reaction occurs or its rate law.Formula: C36H28OP2. In my other articles, you can also check out more blogs about 166330-10-5

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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

Application of 12150-46-8, Children learn through play, and they learn more than adults might expect. Science experiments are a great way to spark their curiosity, get their minds active, and encourage them to do something that doesn’t involve a screen. 12150-46-8, C34H28FeP2. A document type is Article, introducing its new discovery.

Ruthenium(II) complexes with ferrocene-modified arene ligands: Synthesis and electrochemistry

A series of arene-ruthenium complexes of the general formula [RuCl2{eta6-C6H5 (CH2)2R}L] with R=OH, CH2OH, OC(O)Fc, CH2OC(O)Fc (Fc=ferrocenyl) and L=PPh3, (diphenylphosphino)ferrocene, or bridging 1,1?-bis(diphenylphosphino)ferrocene, have been synthesized. Two synthetic pathways have been used for these ferrocene-modified arene-ruthenium complexes: (a) esterification of ferrocene carboxylic acid with 2-(cyclohexa-1,4-dienyl)ethanol, followed by condensation with RuCl3 ¡¤ n H2O to afford [RuCl2 {eta6-C6H5 (CH2)2OC(O)Fc}]2, and (b) esterification between ferrocene carboxylic acid and [RuCl2{eta6 -C6H5(CH2)3OH}L] to give [RuCl2{eta6-C6H5 (CH2)3OC(O)Fc}L]. All new compounds have been characterized by NMR and IR spectroscopy as well as by mass spectrometry. The single-crystal X-ray structure analysis of [RuCl2{eta6-C6H5 (CH2)3OH}(PPh3)] shows that the presence of a CH2CH2CH2OH side-arm allows [RuCl2{eta6-C6H5 (CH2)3OH}(PPh3)] to form an intramolecular hydrogen bond with a chlorine atom. The electrochemical behavior of selected representative compounds has been studied. Complexes with ferrocenylated side arms display the expected cyclic voltammograms, two independent reversible one-electron waves of the Ru(II)/Ru(III) and Fe(II)/Fe(III) redox couples. Introduction of a ferrocenylphosphine onto the ruthenium is reflected by an additonal reversible, one-electron wave due to ferrocene/ferrocenium system which is, however, coupled with the Ru(II)/Ru(III) redox system.

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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

Children learn through play, and they learn more than adults might expect. Science experiments are a great way to spark their curiosity, get their minds active, and encourage them to do something that doesn¡¯t involve a screen. 166330-10-5, C36H28OP2. A document type is Article, introducing its new discovery., Product Details of 166330-10-5

Blue-light emission of Cu(I) complexes and singlet harvesting

Strongly luminescent neutral copper(I) complexes of the type Cu(pop)(NN), with pop = bis(2-(diphenylphosphanyl)phenyl)ether and NN = bis(pyrazol-1-yl) borohydrate (pz2BH2), tetrakis(pyrazol-1-yl)borate (pz4B), or bis(pyrazol-1-yl)-biphenyl-borate (pz2Bph 2), are readily accessible in reactions of Cu(acetonitrile) 4+ with equimolar amounts of the pop and NN ligands at ambient temperature. All products were characterized by means of single crystal X-ray diffractometry. The compounds exhibit very strong blue/white luminescence with emission quantum yields of up to 90%. Investigations of spectroscopic properties and the emission decay behavior in the temperature range between 1.6 K and ambient temperature allow us to assign the emitting electronic states. Below 100 K, the emission decay times are in the order of many hundreds of microseconds. Therefore, it is concluded that the emission stems from the lowest triplet state. This state is assigned to a metal-to-ligand charge-transfer state (3MLCT) involving Cu-3d and pop-pi* orbitals. With temperature increase, the emission decay time is drastically reduced to e.g. to 13 s (Cu(pop)(pz2Bph2)) at ambient temperature. At this temperature, the complexes exhibit high emission quantum yields, as neat material or doped into poly(methyl methacrylate) (PMMA). This behavior is assigned to an efficient thermal population of a singlet state (being classified as 1MLCT), which lies only 800 to 1300 cm-1 above the triplet state, depending on the individual complex. Thus, the resulting emission at ambient temperature largely represents a fluorescence. For applications in OLEDs and LEECs, for example, this type of thermally activated delayed fluorescence (TADF) creates a new mechanism that allows to harvest both singlet and triplet excitons (excitations) in the lowest singlet state. This effect of singlet harvesting leads to drastically higher radiative rates than obtainable for emissions from triplet states of Cu(I) complexes.

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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

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. 166330-10-5, Name is (Oxybis(2,1-phenylene))bis(diphenylphosphine), molecular formula is C36H28OP2. In a Patent£¬once mentioned of 166330-10-5, Quality Control of: (Oxybis(2,1-phenylene))bis(diphenylphosphine)

NOVEL TRANSITION METAL COMPLEX AND PROCESS FOR PRODUCING OPTICALLY ACTIVE ALCOHOL WITH THE COMPLEX

A novel transition metal complex, preferably a ruthenium-phosphine complex or rhodium-phosphine complex, which is effectively usable in various asymmetric syntheses and, in particular, is more effectively usable in the asymmetric hydrogenation of various ketones; and a novel process for producing an optically active alcohol with the complex. The novel transition metal complex includes a ligand obtained by introducing a diarylphosphino group into each of the 2- and 2′-positions of diphenyl ether, benzophenone, benzhydrol, or the like. It preferably further includes an optically active 1,2-diphenylethylenediamine coordinated thereto. The complex preferably is a novel diphosphine-ruthenium-optically active diamine complex or diphosphine-rhodium-optically active diamine complex. The process comprises using the complex as an asymmetric hydrogenation catalyst to conduct the asymmetric hydrogenation of a ketone compound to thereby obtain an optically active alcohol in a high optical purity and a high yield.

Balanced chemical reaction does not necessarily reveal either the individual elementary reactions by which a reaction occurs or its rate law.Quality Control of: (Oxybis(2,1-phenylene))bis(diphenylphosphine). In my other articles, you can also check out more blogs about 166330-10-5

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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