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Chemical and Electrochemical Oxidation of CpRe(PAr3)2H2 Complexes To Give Stable 17-Electron Radical Cations. Disproportionation to Diamagnetic Species via Electron Transfer Catalysis

Oxidations of CpRe(PAr3)2H2 complexes give stable .+ complexes in both acetonitrile and dichloromethane as determined by controlled-potential thin-layer coulometry and double-potential step chronocoulometry.The magnitude of Eo for the Re(III)/Re(IV) couple as detrmined by cyclic voltammetry is influenced by the aryl substituents in the CpRe2 complexes (1: X=H; 3: X=Me; 4: X=F; 5: X=MeO) with Eo becoming more positive as the ?-donating ability of the substituent decreases.Oxidation at more positive potentials presumably produces 2+, a diamagnetic 16-electron species, which reacts with the 17 electron species.This reaction is autocatalytic with the electron-transfer catalysis (ETC), giving current efficiencies of between 5 and 20 for each electron removed beyond the 17-electron species.In acetonitrile, the reaction driven by ETC gave equal amounts of two products, + and +, while in dichloromethane only the latter product was produced.Ferricinium hexafluorophospate oxidation in 1 gave +– (7) in 43percent yield and +– in 45percent yield.The structure of 7 was determined unambiguously by single-crystal X-ray crystallographic analysis.The molecule +– crystallizes in a trans geometry in monoclinic space group P22/c with Z=4, a=9.908(2) Angstroem, b=21.546(9) Angstroem, c=18.967(6) Angstroem, and beta=99.12(2) deg.The + complexes exhibit reversible one-electron oxidations by cyclic voltammetry and show that the magnitude of Eo is once more a function of the electron-donating ability of the aryl substituents.The mechanism of chain propagation in the reactions of the .+ complexes involves either proton transfer or hydrogen atom transfer with the 16-ectron 2+ moieties to give species capable of oxidizing more of the 17-electron complex.

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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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Balanced chemical reaction does not necessarily reveal either the individual elementary reactions by which a reaction occurs or its rate law.HPLC of Formula: C21H21P. In my other articles, you can also check out more blogs about 1038-95-5

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, HPLC of Formula: C21H21P

Synthesis, Characterization, DNA Interaction Study, Antibacterial and Anticancer Activities of New Palladium(II) Phosphine Complexes

A series of palladium(II) complexes with N,N-dimethylthiourea and phosphines [tri-p-tolylphosphine (Tptp), benzyl(diphenyl)phosphine (Bdp), cyclohexyl(diphenyl)phosphine (Cdp)] were synthesized by the direct reaction of K2[(PdCl4)] with the corresponding phosphines and then with N,N-dimethylthiourea at a molar ratio of 1: 2: 2. The general formula of these complexes is [Pd(L1)2(L2)2]Cl2, where L1 = N,N-dimethylthiourea (Dmtu), L2 = Tptp, Bdp, Cdp. The complexes were characterized by elemental analyses, multinuclear NMR (1H, 13C, 31P), and FT-IR. The complex with cyclohexyl(diphenyl)phosphine was also characterized by single crystal X-ray analysis. The spectral and crystallographic data suggest monodentate coordination of dimethylthiourea through the sulfur atom and of the phosphine ligand through the phosphorus atom and distorted square planar environment of palladium(II). The synthesized complexes have been screened for DNAbinding, antibacterial, cytotoxic, and antitumor activities. The complexes show interaction with DNA via intercalative mode. The complexes show good activity against both gram positive and gram negative bacteria as compared to that of a standard drug, Imipenem. Their antitumor activity against MCF7 tumor cell line was found to be comparable with doxorubicin. MTT assay was used to investigate the cytotoxicity of the studied compounds having activity order: 3 > 2 > 1.

Balanced chemical reaction does not necessarily reveal either the individual elementary reactions by which a reaction occurs or its rate law.HPLC of Formula: C21H21P. In my other articles, you can also check out more blogs about 1038-95-5

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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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. 13885-09-1, C24H19P. A document type is Article, introducing its new discovery., name: 2-(Diphenylphosphino)biphenyl

Spectroscopic and Computational Assessment of Silicon’s Electrophilicity in Phosphinosilylium Cations

An experimental method of determining the electrophilicity of silicon in phosphinosilylium cations is reported and compared to Djukic’s DFT method of computing relative intrinsic silylicity, Pi. We also establish linear correlations between silicon electrophilicity and 29Si NMR chemical shifts, DFT-computed silylicities, and the Tolman electronic parameter of the phosphine. These correlations were not universal, as deviations were observed for the most sterically hindered phosphines. Intermolecular silylium transfer experiments between phosphinosilyliums and added phosphines provided a thermodynamic assessment of the electrophilic character at silicon. This confirmed that relative intrinsic silylicity (Pi) and 29Si NMR chemical shifts are useful parameters for semiquantitatively determining the electrophilicity of the silyl group in a Lewis pair.

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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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H-bonded adducts of [2,4,6-{(C10H21O)3C6H2NH}3C3N3] with [LnM{PPh2(C6H4CO2H)}] displaying columnar mesophases at room temperature

Displacement of a labile ligand from appropriate precursor complexes by 2- or 4-PPh2C6H4COOH yields neutral gold(I) and gold(III) [AuXn(PPh2C6H4COOH)] (n = 1, X = Cl; n = 3, X = C6F5), cationic gold(I) [Au(PPh2C6H4COOH)2]-(CF3SO3), and neutral chromium(0) [Cr(CO)5(PPh2C6H4COOH)] metallo-organic acids. [AuCl(4-PPh2C6H4COOH)], [Au(C6F5)3(4-PPh2C6H4COOH)], and [Cr(CO)5(2-PPh2C6H4COOH)] have dimeric structures with typical carboxylic H-bond bridges, whereas [Au(C6F5)3(2-PPh2C6H4COOH)] gives a monomeric species with the carboxylic acid H bonded to cocrystallized solvent molecules. All gold-containing acids are emissive at 77 K in the range 404-520 nm and some of them also at 298 K with emission maxima from 441 to 485 nm. Reaction of these acid metal complexes with the triazine mesogen 2,4,6-{(C10H21O)3C6H2NH}3C3N3 affords some new hydrogen-bonded gold(I) and chromium(0) supramolecular adducts, but the related gold(III) complexes do not form adducts. The 4-diphenylphosphinobenzoic adducts display a columnar hexagonal mesophase (Colhex) at room temperature, with a random one-dimensional stacking of the pseudo-discoid triazine-metallo-organic adducts into columns, where the metallo-phosphinoacid fragments act as the fourth branch of the trifold triazine core. The 2-diphenylphosphinobenzoic mixtures do not display mesophases, as they appear in the X-ray studies as mixtures of the triazine and the metallo-phosphinoacid complex. The aggregates are luminescent at 77 K, with emission maxima in the range 419-455 nm. (Chemical Equation Presented).

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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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Reference of 1038-95-5, 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. 1038-95-5, C21H21P. A document type is Conference Paper, introducing its new discovery.

Benzene hydrogenation over Pt/siliceous zeolites

A comprehensive study has been made on benzene hydrogenation over several zeolite and alumina supported platinum catalysts. It was found that the hydrogenation activity of the supported Pt depends strongly on the support structure, reaction temperature, and Pt content and deposition procedures. For Pt/ZSM-5 (Si/Al = 150), a higher activity was observed for supported Pt prepared by impregnation than ion-exchange method. Consequently, a reverse trend was observed for the methylcyclopentane-to-cyclohexane product ratio, which serves as an indicator for bifunctional catalysis. Selective modifications of Pt/ZSM-5 catalysts using various phosphines as Pt-poisoning agents have been made to identify the locations of the supported Pt. The results correlate well with rate constants and activation energies derived from the zeroth order kinetics model. Furthermore, a highly active Pt/silicalite catalyst has been developed, its potential applications in catalyzing benzene saturation reaction of light reformate in gasoline is also discussed.

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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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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.name: Tri-p-tolylphosphine, you can also check out more blogs about1038-95-5

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Kinetics of Nucleophilic Attack on Co-ordinated Organic Moieties. Part 25. A Nucleophilic Order for Attack upon the + Cation

Kinetic studies of the addition of a range of phosphine and phosphite nucleophiles (PR3) to the cation + to give + adducts reveal the general rate law kobs = k1(PR3).Combination of these results with analogous data for amine and anionic nucleophiles provides the first comprehensive nucleophilicity order for attack on this cycloheptadienyl substrate.For the neutral phosphorus and nitrogen nucleophiles, this nucleophilicity order quantitatively parallels that found for the related but much more reactive + substrate, indicating departure from the reactivity-selectivity principle.However, with N3- the C7H9 cation reveals exceptional reactivity, suggesting a change in mechanism for this anionic nucleophile.

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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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Balanced chemical reaction does not necessarily reveal either the individual elementary reactions by which a reaction occurs or its rate law.Computed Properties of C20H15OP. In my other articles, you can also check out more blogs about 78871-05-3

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. 78871-05-3, Name is Di(naphthalen-2-yl)phosphine oxide, molecular formula is C20H15OP. In a Article£¬once mentioned of 78871-05-3, Computed Properties of C20H15OP

Metal-free photo-induced radical C-P and C-S bond formation for the synthesis of 2-phosphoryl benzothiazoles

We reveal here a visible-light promoted phosphorylation of 2-isocyanoaryl thioethers for the first time with concomitant C(sp3)-S bond cleavage and imidoyl C?S formation. Additionally, this method features the use of 3 mol% organic dye Rose Bengal as the photocatalyst without external transition-metal or peroxide oxidants, and provides a novel and environmentally friendly approach for the preparation of a variety of 2-phosphoryl benzothiazoles in moderate to good yields.

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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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A convenient alternative to prepare phosphine sulfides

An efficient procedure to obtain phosphine sulfides by means of their corresponding phosphines in presence of sodium polisulfide solution, is described. Reaction yields are high and the work-up is very simple.

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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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Balanced chemical reaction does not necessarily reveal either the individual elementary reactions by which a reaction occurs or its rate law.Quality Control of: (R)-1,1-Binaphthyl-2,2-diyl phosphorochloridate. In my other articles, you can also check out more blogs about 155613-52-8

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. 155613-52-8, Name is (R)-1,1-Binaphthyl-2,2-diyl phosphorochloridate, molecular formula is C20H12ClO2P. In a Article£¬once mentioned of 155613-52-8, Quality Control of: (R)-1,1-Binaphthyl-2,2-diyl phosphorochloridate

Chiral palladium bis(phosphite) PCP-pincer complexes via ligand C-H activation

The synthesis of a range of chiral palladium bis(phosphite) pincer complexes has been achieved via C-H activation of the parent ligands and one of the complexes formed shows good activity in the catalytic allylation of aldehydes. The Royal Society of Chemistry 2006.

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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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Asymmetric diosmium sawhorse complexes

Three asymmetric diosmium(I) carbonyl sawhorse complexes have been prepared by microwave heating. One of these complexes is of the type Os2(mu-O2CR)(mu-O2CR? )(CO)4L2, with two different bridging carboxylate ligands, while the other two complexes are of the type Os2(mu-O2CR)2(CO)5L, with one axial CO ligand and one axial phosphane ligand. The mixed carboxylate complex Os2(mu-acetate)(mu-propionate)(CO)4[P(p-tolyl)3]2,(1), was prepared by heating Os3(CO)12 with a mixture of acetic and propionic acids, isolating Os2(mu-acetate)(mu-propionate)(CO)6, and then replacing two CO ligands with two phosphane ligands. This is the first example of an Os2 sawhorse complex with two different carboxylate bridges. The syntheses of Os2(mu-acetate)2(CO)5[P(p-tolyl)3], (3), and Os2(mu-propionate)2(CO)5[P(p-tolyl)3], (6), involved the reaction of Os3(CO)12 with the appropriate carboxylic acid to initially produce Os2(mu-carboxylate)2(CO)6, followed by treatment with refluxing tetrahydro-furan (THF) to form Os2(mu-carboxylate)2(CO)5(THF), and finally addition of tri-p-tolylphosphane to replace the THF ligand with the P(p-tolyl)3 ligand. Neutral complexes of the type Os2(mu-O2CR)2(CO)5L had not previously been subjected to X-ray crystallographic analysis. The more symmetrical disubstituted complexes, i.e. Os2(mu-formate)2(CO)4[P(p-tolyl)3]2,(8), Os2(mu-acetate)2(CO)4[P(p-tolyl)3]2,(4), and Os2(mu-propionate)2(CO)4[P(p-tolyl)3]2,(7), as well as the previously reported symmetrical unsubstituted complexes Os2(mu-acetate)2-(CO)6,(2), and Os2(mu-propionate)2(CO)6,(5), were also prepared in order to examine the influence of axial ligand substitution on the Os?Os bond distance in these sawhorse molecules. Eight crystal structures have been determined and studied, namely mu-acetato-1kO:2kO?-mu-propanoato-1kO:2kO?-bis[tris(4-methyl-phenyl)phosphane]-1kP,2kP?-bis(dicarbonylosmium)(Os?Os) dichloromethane monosolvate, [Os2(C2H3O2)(C3H5O2)(C21H21P)2(CO)4].CH2Cl2, (1), bis(mu-acetato-1kO:2kO? )bis(tricarbonylosmium)(Os?Os), [Os2(C2H3O2)2(CO)6], (2) (redetermined structure), bis(mu-acetato-1kO:2kO? )pentacarbonyl-1k2C,2k3C-[tris(4-methylphenyl)phosphane-1kP]diosmium(Os?Os), [Os2(C2H3O2)2(C21H21-P)(CO)5], (3), bis(mu-acetato-1kO:2kO? )bis[tris(4-methylphenyl)phosphane]-1kP,2kP-bis(dicarbonylosmium)(Os?Os) p-xylene sesquisolvate, [Os2(C2H3O2)2(C21H21P)2-(CO)4].1.5C8H10,(4), bis(mu-propanoato-1kO:2kO? )bis(tricarbonylosmium)(Os?Os), [Os2(C3H5O2)2(CO)6], (5), pentacarbonyl-1k2C,2k3C-bis(mu-propanoato-1kO:2kO? )-[tris(4-methylphenyl)phosphane-1kP]diosmium(Os?Os), [Os2(C3H5O2)2(C21H21P)-(CO)5], (6), bis(mu-propanoato-1kO:2kO? )bis[tris(4-methylphenyl)phosphane]-1kP,2kP-bis(dicarbonylosmium)(Os?Os) dichloromethane monosolvate, [Os2-(C3H5O2)2(C21H21P)2(CO)4].CH2Cl2, (7), and bis(mu-formato-1kO:2kO? )bis-[tris(4-methylphenyl)phosphane]-1kP,2kP-bis(dicarbonylosmium)(Os?Os), [Os2-(CHO2)2(C21H21P)2(CO)4], (8).

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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