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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. 19845-69-3, C30H32P2. A document type is Article, introducing its new discovery., Formula: C30H32P2

Preparation, characterization, and luminescence properties of a 58-electron linear Pt4 cluster, [Pt4(dmb)4(PPh3)2]2+ (dmb = 1,8-diisocyano-p-menthane), and its diphosphine polymers

The title compounds [Pt4(dmb)4(PPh3)2]Cl2 (1) and {[Pt4(dmb)4(diphos)]Cl2}n (diphos = dppb (2), dppp (3), dpph (4)) have been prepared in good yields from the reaction of Pt2(dba)3·CHCl3 with 2 equiv of dmb and 1 equiv of PPh3 for 1 (dba = dibenzylideneacetone) and from the reactions of Pt2(dba)3·CHCl3 with 2 equiv of dmb and 0.5 equiv of diphos for 2-4. The structure for 1 consists of a quasi-linear Pt4L22+ species (L = PPh3; d(PtPt) = 2.666(2), 2.655(2), 2.641(2) A), where the dmb ligands bridge the Pt atoms forming a catenate. From Raman spectroscopy, the two v(PtPt) active modes for 1 are observed at 162 and 84 cm-1 (F(PtPt) = 2.36 mdyn A-1). For 2-4, the diphos ligands induce the formation of amorphous polymeric materials (X-ray powder diffraction patterns) with MW ranging from 84 000 to 307 000 according to viscometry. EHMO calculations predict that the HOMO and LUMO are the two dsigma* orbitals arising from four interacting Pt atoms via the dx2-y2, dz2, s, and px M atomic orbitals. These are mixed with the ddelta and CNR(pi*) MO’s. From the examination of the position, absorptivity, and fwhm (full width at half maximum) of the strongly allowed low-energy UV-vis band, a dsigma* ? dsigma* assignment is made (lambdamax = 405 nm, ? = 35 800 M-1 cm-1; EtOH for 1). The four compounds are luminescent at 77 K in EtOH, where lambdaemi are 750, 736, 750, and 755 nm and taue are 2.71, 4.78, 5.15, and 5.17 ns for 1-4, respectively. On the basis of the Stokes shifts (10 000-12 000 cm-1) and the long emission lifetimes, a phosphorescence dsigma* ? dsigma* assignment is made for the observed emissions. Crystal data for 1: crystal system triclinic; space group P1; a = 12.624(4) A;b = 14.24(2) A; c = 27.312(3) A; alpha = 92.35(3); beta= 91.655(15); gamma = 90.28(5); V = 4903(7) A3; Z = 2; Dcalc = 1.528 g cm-3; R1 = 0.0738; wR2 = 0.2097; S = 1.018.

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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.50777-76-9, Name is 2-(Diphenylphosphino)benzaldehyde, molecular formula is C19H15OP. In a Article,once mentioned of 50777-76-9, name: 2-(Diphenylphosphino)benzaldehyde

Efficient and practical Ag-catalyzed cycloadditions between arylimines and the Danishefsky diene

An efficient Ag-catalyzed method for asymmetric addition of the Danishefsky diene to various aryl imines to afford cycloadducts in ?89% ee and ?85% isolated yield is reported. Reactions are effected with 0.1-1 mol % catalyst (4 C), and the chiral ligand is readily prepared from commercially available materials, including the inexpensive i-Leu. These catalytic asymmetric cycloadditions can be carried out without the use of solvent or with undistilled THF in air. A first generation supported chiral catalyst that effectively promotes the cycloaddition reaction and can be recycled (five cycles) is described. Copyright

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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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Application of 1038-95-5. Let’s face it, organic chemistry can seem difficult to learn. Especially from a beginner’s point of view. Like 1038-95-5, Name is Tri-p-tolylphosphine. In a document type is Article, introducing its new discovery.

Effects of Cyclopentadienyl and Phosphine Ligands on the Basicities and Nucleophilicities of Cp’Ir(CO)(PR3) Complexes

Basicities of the series of complexes CpIr(CO)(PR3) [PR3 = P(p-C6H4CF3)3 P(p-C6H4F)3, P(p-C6H4Cl)3, PPh3, P(p-C6H4CH3)3, P(p-C6H4OCH3)3, PPh2Me, PPhMe2, PMe3, PEt3, PCy3] have been measured by the heat evolved (DeltaHHM) when the complex is protonated by CF3SO3H in 1,2-dichloroethane (DCE) at 25.0 C. The -DeltaHHM values range from 28.0 kcal/mol for CpIr(CO)[P(p-C6H4CF3)3] to 33.2 kcal/mol for CpIr(CO)(PMe3) and are directly related to the basicities of the PR3 ligands in the complexes. For the more basic pentamethylcyclopentadienyl analogs, the -DeltaHHM values range from 33.8 kcal/mol for the weakest base Cp*Ir(CO)[P(p-C6H4CF3)3] to 38.0 kcal/mol for the strongest Cp*Ir(CO)(PMe3). The nucleophilicities of the Cp’Ir(CO)(PR3) complexes were established from second-order rate constants (k) for their reactions with CH3I to give [Cp’Ir(CO)(PR3)(CH3)]+I- in CD2Cl2 at 25.0 C. There is an excellent linear correlation between the basicities (DeltaHHM) and nucleophilicities (log k) of the CpIr(CO)(PR3) complexes. Only the complex CpIr(CO)(PCy3) with the bulky tricyclohexylphosphine ligand deviates dramatically from the trend. In general, the pentamethylcyclopentadienyl complexes react 40 times faster than the cyclopentadienyl analogs. However, they do not react as fast as predicted from electronic properties of the complexes, which suggests that the steric size of the Cp* ligand reduces the nucleophilicities of the Cp*Ir(CO)(PR3) complexes. In addition, heats of protonation (DeltaHHP) of tris(2-methoxyphenyl)phosphine, tris(2,6-dimethoxyphenyl)phosphine, and tris(2,4,6-trimethylphenyl)phosphine were measured and used to estimate pKa values for these highly basic phosphines.

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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 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. 1038-95-5, Name is Tri-p-tolylphosphine, molecular formula is C21H21P. In a Article,once mentioned of 1038-95-5, Application In Synthesis of Tri-p-tolylphosphine

Quenching of a photosensitized dye through single-electron transfer from trivalent phosphorus compounds

Various types of trivalent phosphorus compounds 1 undergo single-electron transfer (SET) to the photoexcited state of rhodamine 6G (Rho+(*)) in aqueous acetonitrile to quench the fluorescence from Rho+(*). The rate constants k(p) for the overall SET process were determined by the Stern-Volmer method. The rate is nearly constant at a diffusion-controlled limit in the region of E( 1/2 )(1) < 1.3 V (vs Ag/Ag+), whereas log k(p) depends linearly on E( 1/2 )(1) in the region of E( 1/2 )(1) > 1.3 V, the slope of the correlation line being -alphaF/RT with alpha = 0.2. The potential at which the change in dependence of log k(p) on E( 1/2 )(1) occurs (1.3 V) is in accordance with the value of E( 1/2 )(Rho+(*)) (1.22 V) that has been obtained experimentally. Thus, the SET step is exothermic when E( 1/2 )(1) < 1.3 V and endothermic when E( 1/2 )(1) > 1.3 V. The alpha-value (0.2) obtained in the endothermic region shows that the SET step from 1 to Rho+(*)is irreversible in this region. Trivalent phosphorus radical cation 1(·+) generated in the SET step undergoes an ionic reaction with water in the solvent rapidly enough to make the SET step irreversible. In contrast, the SET from amines 2 and alkoxybenzenes 3 to Rho+(*) is reversible when the SET step is endothermic, meaning that the radical cations 2(·+) and 3(·+) generated in the SET step undergo rapid ‘back SET’ in the ground state to regenerate 2 and 3.

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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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Cycloaddition of dialkyl (E)-hex-2-en-4-ynedioates to [60]fullerene by phosphane-promoted tandem alpha(delta’)-Michael additions

Organophosphanes promote the [3+2] cycloaddition reactions of dialkyl (E)-hex-2-en-4-ynedioates and [60]fullerene, giving a series of cyclopenteno-fullerenes 3a-k bearing phosphorus ylides. This cycloaddition reaction is initiated by the attack of nucleophilic phosphanes at the alpha(delta’)-C atom of the dialkyl (E)-hex-2-en-4-ynedioate, which generates a 1,3-dipolar species. These 1,3-dipoles then react with C 60 followed by intramolecular cyclization to give cyclopenteno-fullerenes in moderate-to-good yields. In a cyclic voltmmetry study, these novel fullerenes show a larger cathodic shift in their first reduction potential relative to [6,6]phenyl-C61 methyl butyrate, which indicates that these new derivatives possess higher LUMO energy levels.

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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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Effect of Ligand Electronics on the Reversible Catalytic Hydrogenation of CO2 to Formic Acid Using Ruthenium Polyhydride Complexes: A Thermodynamic and Kinetic Study

Hydrogenation of CO2 to formic acid or formates is often carried out using catalysts of the type H4Ru(PR3)3 (1). These catalysts are also active for the reverse reaction, i.e., the decomposition of formic acid to H2 and CO2. While numerous catalysts have been synthesized for reactions in both directions, the factors controlling the elementary steps of the catalytic cycle remain poorly understood. In this work, we synthesize a series of compounds of type H4Ru(P(C6H4R)3)3 containing both electron-donating and electron-withdrawing groups and analyze their influence on the kinetic and thermodynamic parameters of CO2 insertion and deinsertion. The data are correlated with the catalytic performance of the complexes through linear free-energy relationships. The results show that formic acid dissociation from the catalyst is rate-determining during CO2 hydrogenation, while deinsertion is critical for the decomposition reaction.

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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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Convenient Preparation of Tetraarylphosphonium Halides

Tetraarylphosphonium halides, particularly iodides, can be conveniently prepared by the Pd-catalyzed reaction of aryl halides and triarylphosphines in good yields.

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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 2-carbonyl-4-olefin-5-bromo -1,3-oxazine and the application of the synthetic method of the compound of (by machine translation)

The present invention provides 2-carbonyl-4-olefin-5-bromo -1,3-oxazine compounds and its synthetic method and application. The method comprises: the trifluoromethane sulfonic acid scandium/phosphorus-oxygen ligand and partially under the action of the sodium chloride, the compound of the formula I with by reacting a dihydroxy base sea, shown in formula II is 2-carbonyl-4-olefin-5-bromo -1,3-oxazine compounds. The invention of the formula I with different structure compound and shows a dihydroxy base sea because raw materials, the trifluoromethane sulfonic acid scandium/phosphorus-oxygen ligand and partially under the action of the sodium chloride, the effective synthesis of optically active 2-carbonyl-4-olefin-5-bromo -1,3-oxazine compounds. This kind of compound through the past carbo- split-ring can be very convenient to obtain various containing 1,3-azanol the compounds of structure, at the same time can also be in the reaction for the introduction of a olefin and bromine atom, these functional groups can be further transformed, the introduction of other functional group, has great application value. The method of the invention the raw materials are easy to synthesize, mild reaction conditions, the operation is simple, regional high selectivity, enantiomer excess can be up to 99%, the output is high up to 91%. (by machine translation)

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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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Reference of 224311-51-7. Let’s face it, organic chemistry can seem difficult to learn. Especially from a beginner’s point of view. Like 224311-51-7, Name is 2-(Di-tert-Butylphosphino)biphenyl. In a document type is Review, introducing its new discovery.

Forced exo-nido rhoda and ruthenacarboranes as catalyst precursors: A review

Forced exo-nido rhoda and ruthenacarboranes containing monothio and monophosphinocarboranes have been tested as catalyst precursors in different catalytic reactions. The catalyst precursors employed were [Rh(7-SR-8-R?-7,8-C2B9H10)(PPh 3)2] (R=Ph, Et; R’=Ph, Me), [Rh(7-PR2-8-R?-7,8-C2B9H 10)(PPh3)2] (R=Ph, Et, iPr; R?=H, Me), [Rh(7-PPh2-8-Me-7,8-C2B9H10)(cod)], [Rh(7-SR-8-R?-7,8-C2B9H10)(cod)], [RuX(7-PR2-8-R?-7,8-C2B9H 10)(PPh3)2] (X=Cl, H; R=Ph; R?=H, Me, Ph) and [RuCl(7-SR-8-R?-7,8-C2B9H10)(PPh 3)2] (R=Ph, Et; R?=Me, Ph). These complexes are obtained by the reaction of the tetramethylammonium or cesium salt of the nido ligand with Rh(I) or Ru(II) complexes incorporating ancillary ligands. Although two molecular structures are possible, the closo and the exo-nido, only the exo-nido tautomer is generally formed. The cluster is coordinated to the metal through the S or P atom and one or two B-H-M interactions, depending on the metal. These exo-nido rhoda and ruthenacarboranes have been shown to catalyze in very good yield the hydrogenation of terminal alkenes but they are not active in the hydrogenation of internal alkenes. Both rhoda-monothio and monophosphinocarboranes present comparable activity at P=45 bar and T=66C, in the hydrogenation and isomerization of 1-hexene. However, while the monothioether precursors are active at P=1 atm and T=25C, the monophosphino exhibited a very low activity. Ruthenamonophosphinocarboranes are also active in the hydrogenation of 1-hexene, with a higher selectivity that the respective rhodacarboranes. On the other hand, [Rh(7-PPh2-8-R?-7,8-C2B9H 10)(PPh3)2] (R?=H, Me) catalyze the hydrogenation of methacycline to doxycycline with high yield (ca. 100%) and very high diastereoselectivity, ruthenacarboranes are not active. All these complexes are recoverable after completion of the catalytic reaction. These exo-nido rhoda and ruthenacarboranes displayed a very low activity in the hydrogenation of internal alkenes, however, the closo species [closo-3-(C8H13)-1-SR-2-R?-3,2,1-RhC 2B9H9] (R=Ph; R?=Me, Ph) obtained from [Rh(7-SR-8-R?-7,8-C2B9H10)(cod)] were very efficient catalysts in the hydrogenation of cyclohexene exhibiting higher activity than the parent exo-nido isomers. In addition to hydrogenation, exo-nido rhoda and ruthenamonothio and monophosphinocarboranes have also been tested as catalyst precursors in the insertion of carbenes to C=C and O-H bonds. The rhodamonophosphinocarboranes exhibited a high activity and similar stereoselectivity for the cyclopropanation of olefines (80-90%) and represent the first example of Rh(I) cyclopropanation catalysts. Furthermore, ruthenacarboranes are excellent cyclopropanation catalysts for activated olefins such as styrene and their derivatives while the cyclopropane yields were lower for cyclic olefins and terminal linear monoolefines

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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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In an article, published in an article, once mentioned the application of 213697-53-1, Name is 2′-(Dicyclohexylphosphino)-N,N-dimethyl-[1,1′-biphenyl]-2-amine,molecular formula is C26H36NP, is a conventional compound. this article was the specific content is as follows.Computed Properties of C26H36NP

Synthesis of Substituted 4-, 5-, 6-, and 7-Azaindoles from Aminopyridines via a Cascade C-N Cross-Coupling/Heck Reaction

A practical palladium-catalyzed cascade C-N cross-coupling/Heck reaction of alkenyl bromides with amino-o-bromopyridines is described for a straightforward synthesis of substituted 4-, 5-, 6-, and 7-azaindoles using a Pd2(dba)3/XPhos/t-BuONa system. This procedure consists of the first cascade C-N cross-coupling/Heck approach toward all four azaindole isomers from available aminopyridines. The scope of the reaction was investigated and several alkenyl bromides were used, allowing access to different substituted azaindoles. This protocol was further explored for N-substituted amino-o-bromopyridines.

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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