09/18/21 News Can You Really Do Chemisty Experiments About 1,1-Bis(diphenylphosphino)ferrocene

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Previous reports in the literature have established the utility of 1,1?-bis(diphenylphosphino)ferrocene (DPPF, LPh) in the nickel-catalyzed cross-coupling of (hetero)aryl electrophiles with primary or secondary amines. In an effort to evaluate the effect of varying the PR2-donor groups on catalytic performance in such transformations, a series of 10 structurally varied 1,1?-bis(bis(alkyl/aryl)phosphino)ferrocene ancillary ligands (LX) were systematically examined in selected competitive test cross-couplings of (hetero)aryl halides with furfurylamine, morpholine, and indole employing Ni(COD)2/LX catalyst mixtures. In addition to the excellent performance observed for the parent ligand LPh in a number of the test transformations explored, selected dialkylphosphino (e.g., DiPPF, LiPr) and meta-disubstituted diarylphosphino variants of LPh also proved highly effective. In particular, the electron-deficient ligand variant LCF3 featuring 3,5-bis(trifluoromethyl)phenyl groups on phosphorus was found to exhibit superior catalytic performance relative to LPh in most of the test transformations involving the N-arylation of indole. Our efforts to prepare Ni(II) precatalysts of the type (LX)Ni(o-tolyl)Cl, in analogy with known (LPh)Ni(o-tolyl)Cl, by employing several literature methods met with mixed results. Whereas (LiPr)Ni(o-tolyl)Cl was prepared straightforwardly and was crystallographically characterized, the use of LCF3 or ligands featuring tert-butyl (LtBu), o-tolyl (Lo-tol), or 4-methoxy-3,5-dimethylphenyl (LOMe) groups on phosphorus under similar conditions resulted in poor conversion to product and/or the formation of poorly soluble materials, highlighting the limitations of this commonly used precatalyst design.

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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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Thermal decomposition of the palladium (aryl)neopentoxide complexes [P-P]Pd(Ar)OCH2CMe3 [P-P =Tol-BINAP or BINAP; Ar p-C6H4CHO (1b), p-C6H4COPh (1c), p-C6H4NO2 (1d), o-C6H4NO2 (1e), o-C6H4CN (1F)] possessing substituents on the palladium-bound aryl group suitable for delocalization of negative charge led to quantitative (?95%) formation of aryl ether without detectable beta-hydride elimination. Thermal decomposition of 1b-f obeyed first-order kinetics, and the rate of reductive elimination decreased in the order o-NO2 > p-NO2 > p-CHO > p-COPh > o-CN. Conversely, thermal decomposition of the related derivatives [P-P]Pd(Ar)OCH2CMe3 [P-P = Tol-BINAP or BINAP; Ar p-C6H4Cl (1g), m-C6H4NO2 (1h), m-C6H4CN (1i)] which did not possess a resonance stabilizing group on the palladium-bound aryl group led to no detectable formation of aryl ether. These and related data point to the buildup of negative charge in the palladium-bound aryl group in the transition state for C-O reductive elimination and are consistent with a mechanism initiated by inner-sphere nucleophilic attack of the alkoxide ligand at the ipso-carbon atom of the palladium-bound aryl group through a zwitterionic Meisenheimer-type intermediate or transition state.

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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

Sep-21 News Extracurricular laboratory:new discovery of 1,1-Bis(diphenylphosphino)ferrocene

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Treatment of diphosphines Ph2P(CH2) nPPh2 (n = 1, 2, 4, 6) and [Fe(eta5-C 5H4PR?2)2] (R? = Ph, iPr) with a two-fold excess of (RO)2P(S)N3 (R = Et, Ph) results in the high-yield formation of the N-thiophosphorylated bis(iminophosphorane) derivatives (CH2)n[P{NP(S)(OR) 2}Ph2]2 and Fe(eta5-C 5H4[P{NP(S)(OR)2}R?2]) 2, respectively. The reactions of these ligands with AgSbF 6 in a 1: 1 molar ratio have been investigated. The resulting silver(i) complexes, derived from the selective coordination of the PS units, have been characterized by IR, NMR and MS (FAB) spectroscopy and, in selected cases, by X-ray crystallography. Monomeric, dimeric and polymeric solid-state structures, depending on the nature of the ligand backbone, have been found. The Royal Society of Chemistry 2007.

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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

Sep-21 News New explortion of 1,1-Bis(diphenylphosphino)ferrocene

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Intermolecular hydroarylation reactions of highly strained methylenecyclopropanes 2-phenylmethylenecyclopropane (1), 2,2- diphenylmethylenecyclopropane (2), methylenespiropentane (3), bicyclopropylidene (4), (dicyclopropylmethylene)cyclopropane (5), and benzhydrylidenecyclopropane (6) through C-H bond functionalization of 2-phenylpyridine (7 a) and other arenes with directing groups were studied. The reaction was very sensitive to the substitution on the methylenecyclopropanes. Although these transformations involved (cyclopropylcarbinyl)-metal intermediates, substrates 1 and 4 furnished anti-Markovnikov hydroarylation products with complete conservation of all cyclopropane rings in 11-93 % yield, whereas starting materials 3 and 5 were inert toward hydroarylation. Methylenecyclopropane 6 formed the products of formal hydroarylation reactions of the longest distal C-C bond in the methylenecyclopropane moiety in high yield, and hydrocarbon 2 afforded mixtures of hydroarylated products in low yields with a predominance of compounds that retained the cyclopropane unit. As byproducts, Diels-Alder cycloadducts and self-reorganization products were obtained in several cases from substrates 1-3 and 5. The structures of the most important new products have been unambiguously determined by X-ray diffraction analyses. On the basis of the results of hydroarylation experiments with isotopically labeled 7 a-[D5], a plausible mechanistic rationale and a catalytic cycle for these unusual ruthenium-catalyzed hydroarylation reactions have been proposed. Arene-tethered ruthenium-phosphane complex 53, either isolated from the reaction mixture or independently prepared, did not show any catalytic activity. 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

Sep 2021 News Extracurricular laboratory:new discovery of 1,1-Bis(diphenylphosphino)ferrocene

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Efficient syntheses and characterization of a platinum metallacyclyne containing one cyclic enyne pocket (3), the first dinuclear platinum metallacyclyne containing two cyclic enyne pockets (4), and 2,2?,6,6?-tetraethynyltolan (2) are reported. Syntheses of 3 and 4 employ bidentate phosphines or cis-platinum starting materials and high dilution techniques to effect high 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

Sep 2021 News Awesome Chemistry Experiments For 1,1-Bis(diphenylphosphino)ferrocene

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A series of tetranuclear heterothiometallic clusters [Et4N] 2[(MS4)2Au2(dppe)] (1: M = Mo; 2: M = W), [PPh4]2[(MoOS3)2Au 2(dppe)] (3), [Et4N]2[(WOS3) 2Au2(dppe)] (4) (dppe = 1,2-bis(diphenylphosphino)ethane), [Et4N]2[(MS4)2Au2(dppf)] (5: M = Mo; 6: M = W) and [Et4N]2[(MOS3) 2Au2(dppf)] (7: M = Mo; 8: M = W) (dppf = 1,1?-bis(diphenylphosphino)ferrocene) have been synthesized from the reactions of thiometalates [MXS3]2- (M = Mo or W, X = O or S), AuCl(SC4H8) and dppe or dppf. The crystal structures of the complexes 2, 4 and 6 have been determined by single-crystal X-ray diffraction studies. In the molecular structures of these complexes, the two linear M/Au/S units are linked via bidentate phosphines dppe or dppf. The complexes have been fully characterized by IR, UV-vis as well as elemental analyses. These clusters all exhibit room-temperature luminescence in the solid state.

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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

Sep 2021 News Brief introduction of 1,1-Bis(diphenylphosphino)ferrocene

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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.12150-46-8, Name is 1,1-Bis(diphenylphosphino)ferrocene, molecular formula is C34H28FeP2. In a Patent,once mentioned of 12150-46-8, Application In Synthesis of 1,1-Bis(diphenylphosphino)ferrocene

Ferrocenyldiphosphin-ruthenium complexes are new and good catalysts for the hydrogenation of exocycilc double bond of d-Thiophene 3 to d-Thiophane4, both of which are intermediates of D-Biotin 1 synthesis. in which R signifies -OCH3(3a), -OCH2CH3(3b), -CH2COOH(3c), -CH2COOCH3(3d) or -CH2COOEt(3e) and Bz signifies benzyl group

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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

10/9/2021 News Can You Really Do Chemisty Experiments About 1,1-Bis(diphenylphosphino)ferrocene

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

Three ruthenium complexes [RuCl(CTZ)(bipy)(P-P)]PF6 [P-P = 1,2-bis(diphenylphosphino)ethane (dppe-1), 1,4-bis(diphenylphosphino)butane (dppb-2) and 1,1?-bis(diphenylphosphino)ferrocene (dppf-3), bipy = 2,2?-bipiridine and clotrimazole (CTZ) 1-[(2-chlorophenyl)diphenylmethyl]-1H-imidazole] were synthesized. These complexes were characterized by a combination of elemental analysis, molar conductivity, infrared and UV?vis spectroscopy, 1H, 13C{1H} and 31P{1H} nuclear magnetic resonance techniques, cyclic voltammetry and mass spectroscopy. Bovine serum albumin binding constants, which were in the range of 1.30?36.00 × 104 M? 1, and thermodynamic parameters suggest spontaneous interactions with this protein by electrostatic forces due to the positive charge of the complexes. DNA interactions studied by spectroscopic titration, viscosity measurements, gel electrophoresis, circular dichroism, ethidium bromide displacement and reactions with guanosine and guanosine monophosphate indicated the DNA binding affinity primarily through non-covalent interactions. All complexes 1?3 were tested against the human carcinoma cell lines MCF-7 (breast), A549 (lung) and DU-145 (prostate) presenting promising IC50 values, between 0.50 and 14.00 muM, in some cases lower than the IC50 for the reference drug (cisplatin). The antimicrobial activity assays of the complexes provided evidence that they are potential agents against mycobacterial infections, specifically against Mycobacterium tuberculosis H37Rv.

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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

Sep 2021 News Top Picks: new discover of 1,1-Bis(diphenylphosphino)ferrocene

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The electrochemical oxidation of 1,1′-bis(diphenylphosphino)ferrocene (dppf) at a platinum electrode in 1,2-dichloroethane has been studied by cyclic voltammetry, controlled potential electrolysis, and 31P NMR spectroscopy.The compound undergoes a ferrocene-based reversible oxidation, which is followed by a fast chemical reaction, involving the phosphorus substituent on the cyclopentadienyl rings, to give dppfO, dppfO2, dppfH+ and dppfH22+.Kinetic data suggest that the reaction involves a reversible intramolecular electron transfer between the ferrocene core and the electron-rich substituents to give a phosphinium radical ion, which undergoes a second order rate-determining dimerization or a reaction with the parent compound to give a ferrocenylphosphine dimer cation radical, the ultimate fate of which is the formation of protonated and oxygenated dppf derivatives by nucleophilic attack by water present in the reaction medium.Evidence for the formation of the transient monomeric phosphinium radical was obtained by trapping it with 1,1′-diphenylethylene to give phosphorus-bonded monoalkene adducts of dppf.

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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

Sep 2021 News New explortion of 1,1-Bis(diphenylphosphino)ferrocene

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12150-46-8, Name is 1,1-Bis(diphenylphosphino)ferrocene, molecular formula is C34H28FeP2, belongs to chiral-phosphine-ligands compound, is a common compound. In a patnet, once mentioned the new application about 12150-46-8, HPLC of Formula: C34H28FeP2

Heterobimetallic ferrocenylthiosemicarbazone palladium(II) complexes (3-5) were prepared through the cleavage of a chlorido-bridged palladium ferrocenylthiosemicarbazone intermediate (2) using various P-donor ligands. These compounds were screened for antiplasmodial activity against chloroquine-sensitive (NF54) and chloroquine-resistant (Dd2) Plasmodium falciparum strains, exhibiting biological activity in the low micromolar range. The compounds generally display well-resolved electrochemically reversible one-electron transfer processes for the ferrocenyl group. The half-wave potential for the Fe(II)/Fe(III) couple is electronically influenced by the type of P-donor group through the palladium(II) centre.

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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