Extracurricular laboratory:new discovery of Tri-p-tolylphosphine

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Reaction of the tetrakis(cyclooctene)rhodium(I) complex [{Rh(C8H14-c)2(mu-Cl)}2] with the appropriate divinyldisiloxane molecules (ViSiR2)2O (R=Me or Ph) yields, by displacement of the cycloctene ligands, the complexes [{Rh(ViSiR2)2O(mu-Cl)}2] (R=Me (1) or Ph (2)). These react further with a tertiary phosphine PR3 to give cis-[Rh{(ViSiR2)2O}(PR?3)Cl] (R?=Ph or C6H4Me-p). The complex cis-[{Rh(Vi2SiMe2)(mu-Cl)}2] (7) was similarly prepared by the displacement of ethylene from [{Rh(C2H4)2(mu-Cl)}2] by the divinyldimethylsilane Vi2SiMe2. X-ray molecular structures of the crystalline complexes 1, 2 and 7 show a distorted square planar Rh(I) environment, the CH2=CH groups being orthogonal to this plane; 1 and 2 have the Rh-(ViSiR2)2O metallacycle in the chair conformation, but differ in the nature of the central Rh(Cl)RhCl core, which is planar for 1 and puckered for 2, but each of 1 and 2 is the rac-diastereoisomer, whereas 7 has the meso-configuration. In solution 1 and 2 exist as a mixture of isomers, probably the rac- and meso-pairs as established by multinuclear NMR spectral studies. A series of saturation transfer NMR spectroscopic experiments showed that the divinyldisiloxane ligands in [{Rh(ViSiPh2)2O(mu-Cl)}2] underwent a dynamic process involving the dissociation, rotation and then reassociation of the vinyl groups.

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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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Dialkylaminocarbene complexes (CO)5MC(NR2)SiR’3 (1-3) (M = Cr, Mo, W; SiR’3 = SiPh3, SiPh2Me, SiPhMe2; NR2 = NMe2, NMeEt, NC4H8, NC5H10) are obtained by reaction of (CO)5MC(OEt)SiR’3 with HNR2.If the sterically more demanding amines HNEt2, HNBunMe or HN(CH2Ph)Me are used, monoalkylamino-substituted carbene complexes (CO)5MC(NHR)SIR’3 are formed instead, owing to cleavage of one of the organic substituents at nitrogen.However, diethyl-amino-substituted carbene complexes can be synthetized by reaction of the anionic complexes Li<(CO)5MC(NEt)SiR'3> with Et3O+ and show no unusual chemical behaviour.The anionic complexes are prepared by deprotonation of (CO)5MC(NHEt)SiR’3.On heating the pentacarbonyl complexes 1-3 to 100-150 deg C, in the case of some of the chromium and molybdenum complexes already during their synthesis, a cis-CO ligand is lost to give the stable 16-electron carbene complexes (CO)4MC(NR2)SiR’3 (8-10).An X-ray structure analysis of (CO)4WC(NC5H10)SiPh3 (8d) reveals that the empty coordination site that results is screened by a phenyl substituent and that relaxation of the steric strain induced by the bulky carbene ligand, seems to be the driving force for the formation of the 16-electron species.In solution the 16-electron complexes 8-10 are fluxional.In a CO atmosphere the complexes 8-10 are retransformed quantitatively into the pentacarbonyl complexes 1-3.Reaction of (CO)4WC(NMe2)SiPh3 (8a) with methyl isonitrile or phosphines exclusively yields cis-substituted (CO)4LWC(NMe2)SiPh3 (L = MeNC, PR3).

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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 Di(adamantan-1-yl)phosphine

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Iron-chloride, -dinitrogen, and -methyl complexes bearing anionic carbazole-based PNP-type pincer ligands are designed, prepared and characterized by X-ray analysis. Some iron complexes are found to work as catalysts toward nitrogen fixation under mild reaction 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

A new application about Diphenyl(o-tolyl)phosphine

Balanced chemical reaction does not necessarily reveal either the individual elementary reactions by which a reaction occurs or its rate law.COA of Formula: C19H17P. In my other articles, you can also check out more blogs about 5931-53-3

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. 5931-53-3, Name is Diphenyl(o-tolyl)phosphine, molecular formula is C19H17P. In a Article,once mentioned of 5931-53-3, SDS of cas: 5931-53-3

In a previous report (S. Yasui, S. Tojo and T. Majima, J. Org. Chem., 2005, 70, 1276), we presented the results from the laser flash photolysis (LFP) and product analysis of the 9,10-dicyanoanthracene (DCA)-photosensitized oxidation of triarylphosphine (Ar3P) in acetonitrile under air, which showed that the photoreaction results in the oxidation of Ar3P to give the corresponding phosphine oxide (Ar3PO) in a nearly quantitative yield, and that the reaction is initiated by the electron transfer (ET) from Ar 3P to DCA in the singlet excited state (1DCA*), producing the triarylphosphine radical cation Ar3P+. This radical cation decays through radical coupling with O2 to afford the peroxy radical cation Ar3P+-O-O, which we proposed to be the intermediate leading to the product Ar3PO. We now examined this photoreaction in more detail using ten kinds of Ar3P with various electronic and steric characteristics. The decay rate of Ar3P + measured by the LFP was only slightly affected by the substituents on the aryl groups of Ar3P. During the photolysis of trimesitylphosphine (Mes3P), the peroxy radical cation intermediate (Mes3P+-O-O) had a lifetime long enough to be spectrophotometrically detected. The quantum yields of Ar3PO increased with either electron-withdrawing or -releasing substituents on the aryl groups, suggesting that a radical center is developed on the phosphorus atom during the step when the quantum yield is determined. In addition, the o-methyl substituents in Ar3P decreased the quantum yield. These results clearly indicated that Ar3P+-O-O undergoes radical attack upon the parent phosphine Ar3P that eventually produces the final product, Ar3PO. The Royal Society of Chemistry 2006.

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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 series of new dibenzophosphoranes (1-6) bearing uncommon functions such as hydroxy-, alkoxy-, oxo-, amide- and dihydride- attached to the phosphorus atom have been prepared and characterized.The reactivities of the alkoxy derivative 1 and the amide 2 towards alcohols, amines, water and borane were studied mainly by 31P NMR.The structure of the diphenoxyamine-bis-phosphorane 4 was established by single crystal X-ray diffraction studies.

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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.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, Product Details of 161265-03-8

The first efficient and general nickel-catalyzed hydrocyanation of terminal alkynes with Zn(CN)2 in the presence of water has been developed. The reaction provides a regioselective protocol for the synthesis of functionalized vinyl nitriles with a range of structural diversity under mild reaction conditions while obviating use of the volatile and hazardous reagent of HCN. Deuterium-labeling experiments confirmed the role of water as the hydrogen source in this hydrocyanation 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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Two novel chiral thiophosphoramides and two chiral phosphoramidites were synthesized starting from (S)-alpha-phenylethylamine and (R)-(+) or (S)-(-)-1,1′-Bi-2-naphthol (BINOL), respectively, and their application in combination with Lewis acid as cocatalysts in asymmetric Morita-Baylis-Hillman (MBH) reaction was investigated. Dramatic rate acceleration (the corresponding adducts were obtained in fair to excellent chemical yield within 15 min-5 h) was observed in these chiral phosphorus reagents/Lewis acid cocatalyzed MBH reaction between 4-nitrobenzaldehyde and activated alkenes, and in one case, moderate enantioselectivity was achieved (the corresponding adduct’s ee value is 44%). Copyright Taylor and Francis Group, LLC.

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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.15929-43-8, Name is Bis(4-(trifluoromethyl)phenyl)phosphine oxide, molecular formula is C14H9F6OP. In a Article,once mentioned of 15929-43-8, Recommanded Product: 15929-43-8

The three-component reaction of p-quinone monoacetals, amines and diarylphosphine oxides is developed to afford m-(diarylphosphinyl)anilides in moderate to high yields. The reaction may proceed via a process involving phospha-nucleophilic addition to an iminoquinone acetal intermediate and/or carbonyl-amine condensation with a phosphinyl enone intermediate.

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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 240417-00-9, Name is 2-Diphenylphosphino-2′-(N,N-dimethylamino)biphenyl,molecular formula is C26H24NP, is a conventional compound. this article was the specific content is as follows.Computed Properties of C26H24NP

In an attempt to resolve ambiguities in and contradictions among previous studies, NMR spectra of the methylviologen (MV2+), benzylviologen (BV2+), and diquat (DQ2+) dications and ESR spectra of the corresponding cation radicals were reinvestigated.ESR spectra of the cation radicals in methanol solution had sufficiently good signal-to-noise ratios and resolution to permit completely unambiguous determinations of hyperfine coupling constants.ESR intensity data showed that MV+. and BV+. precipitate as ESR-inactive solids at low temperature and that MV+. associates to micelle-like solution particles at high concentration.The intensity data show no evidence for formation of dimers or other low molecular weight polymers.Literature reports of dimer formation in methanol solution are the result of temperature-dependent saturation of the ESR spectra.Line broadening of NMR spetra of MV2+, BV2+, or DQ2+ in the presence of traces of cation radical was used to provide unambiguous assignments of ESR hyperfine coupling constants, and to give good estimates of the cation radical concentrations and the dication/cation radical electron exchange rate constant.The NMR line broadening experiments also provide an estimate of the rate of conformational change of the ethylene bridge in the diquat cation radical.

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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 of silver(I) bromide with tri(p-tolyl)phosphine in MeCN solution in 1:1 molar ratios resulted in a complexes of the formula [AgBr{P(4-MeC6H4)3}]4. This compound has a tetrameric structure with a concave coordination polyhedron, in between a cube and a stella quadrangula. Weak silver-silver interactions were observed. The current compound is compared to the Cl and I analogs using distance-distance plots. The silver-silver interactions seem to dominate the geometry of these tetrameric type of 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