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To determine the trans effect on the rates of reductive eliminations from arylpalladium(II) amido complexes, the reactions of arylpalladium amido complexes bearing symmetrical and unsymmetrical DPPF (DPPF = bis(diphenylphosphino)ferrocene) derivatives were studied. THF solutions of LPd(Ar)(NMeAr?) (L = DPPF, DPPF-OMe, DPPF-CF3, DPPF-OMe,Ph, DPPF-Ph,CF3, and DPPF-OMe,CF3; Ar = C6H 4-4-CF3; Ar? = C6H4-4-CH 3, Ph, and C6H4-4-OMe) underwent C-N bond forming reductive elimination at -15 C to form the corresponding N-methyldiarylamine in high yield. Complexes ligated by symmetrical DPPF derivatives with electron-withdrawing substituents on the DPPF aryl groups underwent reductive elimination faster than complexes ligated by symmetrical DPPF derivatives with electron-donating substituents on the ligand aryl groups. Studies of arylpalladium amido complexes containing unsymmetrical DPPF ligands revealed several trends. First, the complex with the weaker donor trans to nitrogen and the stronger donor trans to the palladium-bound aryl group underwent reductive elimination faster than the regioisomeric complex with the stronger donor trans to nitrogen and the weaker donor trans to the palladium-bound aryl group. Second, the effect of varying the substituents on the phosphorus donor trans to the nitrogen was larger than the effect of varying the substituents on the phosphorus donor trans to the palladium-bound aryl group. Third, the difference in rate between the isomeric arylpalladium amido complexes was similar in magnitude to the differences in rates resulting from conventional variation of substituents on the symmetric phosphine ligands. This result suggests that the geometry of the complex is equal in importance to the donating ability of the dative ligands. The ratio of the differences in rates of reaction of the isomeric complexes was similar to the relative populations of the two geometric isomers. This result and consideration of transition state geometries suggest that the reaction rates are controlled more by substituent effects on ground state stability than on transition state energies. In addition, variation of the aryl group at the amido nitrogen showed systematically that complexes with more electron-donating groups at nitrogen undergo faster reductive elimination than those with less electron-donating groups at nitrogen.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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The reaction of 1,1?-diacetylferrocene with the dimethylformamide dimethyl acetal proceeds regioselectively to afford [1-acetyl-1?-(1- dimethylamino-3-oxoprop-1-en-3-yl)]ferrocene, based on which new approaches to the synthesis of 1,1?-disubstituted unsymmetrical ferrocene derivatives via the reaction with nucleophilic reagents hydrazine hydrate, hydroxylamine, and amidines were developed.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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The pyrazinium salt [FcCH2pyz][BF4] (1) and the quinoxalinium salt [FcCH2quin][BF4] (2) were prepared by the reaction of [FcCH2][BF4] with pyrazine and quinoxaline, respectively and characterised by spectroscopic methods, cyclic voltammetry and by single-crystal X-ray diffraction, which revealed the absence of any pi-pi-stacking motifs in the crystal structures.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Ferrocenyl thiols of the formula STR1 wherein n is an integer of from 2 to 4 are prepared by reacting a compoundf the formula STR2 with thioacetic acid, STR3 at elevated temperatures in the presence of a free radical initiator to produce a thiol ester of the formula STR4 and then hydrolyzing the thiol ester to produce the thiol. The thiols are useful as non-migrating burning rate modifiers for unsaturated rubber-based propellants.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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The invention discloses a chiral ferrocenesulfonic such P, P method for synthesizing of the ligand, belonging to the field of organic synthesis. This method is realized by the following steps : (1) with vinyl ferrocene as the starting material, chiral under the action of catalyst, and the two disclosed reaction to obtain (R) -1 the […] ferrocenesulfonic yl group II alkyl phosphine ; (2) (R) -1 the radicals […] ferrocenesulfonic yl acetate is disclosed and diethyl zinc reaction and the diphenyl phosphine reaction to obtain the chiral ferrocenyl such P, P ligand (R)-(-) – 1 the […] [(S) -2 the […] (mortars; concrete ; artificial stone) ferrocene] ethyl b is disclosed. Compared with the prior art, the present invention of fewer steps, the operation is simple, high yield, is more suitable for industrial production. Such chiral ferrocenyl made of P, P compounds can be used as the ligand of metal catalyst, used in the medical field. (by machine translation)

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Compounds of Formula (I), compositions containing them, their use in therapy, including their use as antibacterials, for example in the treatment of tuberculosis, and methods for the preparation of such compounds, are provided.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Polyamide aerogels with ferrocene as a monomer repeat unit were prepared in one step from ferrocene dicarboxylic acid and tris(4-isocyanatophenyl)methane. Pyrolysis at ?800 C yielded nanoporous carbons doped throughout with crystallites of alpha-Fe (about 50 nm in diameter), which in turn were shrouded in graphitic ribbons (<30 graphene layers thick). Transmetalation was carried out with aqueous solutions of Au, Pt, Pd, Rh, and Ni salts, via a path akin to galvanic corrosion, whereas graphitic ribbons separated anodes (alpha-Fe particles) from cathodes (defects along the ribbons). The new metallic phases formed clusters of smaller crystallites (10-20 nm in diameter) on the graphitic ribbons, leaving behind empty cage-like formations previously occupied by the Fe(0) nanoparticles. All metal-doped carbons were monolithic and over 85% porous. Catalytic activity was demonstrated with the oxidation of benzyl alcohol to benzaldehyde catalyzed with carbon-supported Au or Pt, the reduction of nitrobenzene by hydrazine to aniline catalyzed with carbon-supported Fe, and two Heck coupling reactions of iodobenzene with styrene or butyl acrylate, catalyzed with carbon-supported Pd. The distinguishing feature of those catalysts was that they could be just picked up, for example, with a pair of tweezers, and redeployed in a new reaction mixture immediately, thus bypassing less efficient recovery processes like filtration. You can also check out more blogs about1111-67-7 and wish help many people in the next few years. .Synthetic Route of 1273-94-5

Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Dehydrogenation of alcohols by three iridium pincer complexes, IrH(Cl)[2,6-(tBu2PO)2C6H 3] (1), {IrH(acetone)[2,6-(tBu2PO) 2C6H3]}{BF4} (2), and IrH(Cl)[{2,5-(tBu2PCH2)2C 5H2}Ru(C5H5)] (3), is reported, in both the presence and the absence of a sacrificial hydrogen acceptor. Dehydrogenation of secondary alcohols proceeds in a catalytic mode with turnover numbers up to 3420 (85% conversion) for acceptorless dehydrogenation of 1-phenylethanol. Primary alcohols are readily decarbonylated even at room temperature to give catalytically inactive 16e Ir-CO adducts. The mechanism of this transformation was studied in detail, especially for EtOH; new intermediates were isolated and characterized.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Treatment of lithium(1-dimethylamino-ethenyl)cyclopentadienide (5a) with FeCl2 generated the corresponding substituted ferrocene (2a) that rapidly underwent cyclization in a subsequent Mannich-type condensation reaction to yield the unsaturated dimethylamino-substituted [3]ferrocenophane 3a. The treatment of 1,1?-diacetylferrocene (1) with dimethylamine, diethylamine or piperidine in the presence of TiCl4 resulted in the formation of the analogously structured functionalized [3]ferrocenophanes 3a-3c, respectively, by a related intramolecular enamine-condensation pathway (complexes 3a and 3b were characterized by X-ray diffraction). Catalytic hydrogenation of 3a-c in THF at Pd/C gave the corresponding saturated amino-substituted [3]ferrocenophane systems 6a-c. The catalytic hydrogenation proceeds trans-product selectively with trans-6-cis-6 ratios ranging between ca. 5:1 and 7:1 for these examples (the complexes trans-6a·HCl, trans-6b, and trans-6c were characterized by X-ray crystal structure analysis). Quaternization of 6a by treatment with methyliodide followed by the reaction with pyrrolidine led to amine exchange at the [3]ferrocenophane framework with the formation of 6d. The amine exchange proceeds stereoselectively with a predominant overall retention (the trans-6d-cis-6d ratio obtained is again ca. 7:1). The complex trans-6d was characterized by X-ray diffraction.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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In this paper, authors focus the synthesis of conjugated unsymmetrical stilbenoid dendrimers by Heck and Horner-Wadsworth-Emmons coupling. In UV?visible absorption spectrum, the intensity of the absorption increases with increase in the generation of dendrimers. Further, bathochromic shift is observed on increasing the generation of the dendrimer from zero to first due to the greater widening of the energy gap between pi-pi* orbitals of the dendrimer system. Interfacial charge transport kinetics such as resistance, chemical capacitance and relaxation lifetime of the fabricated dye-sensitized solar cells (DSSC) are investigated using Nyquist and Bode phase plots by electrochemical impedance spectroscopy. Reduced electron relaxation lifetime (taue) of 1.83 ms (LiI + 7) and 1.04 ms (LiI + 8) provides efficient charge injection and thus reducing recombination process in the device. The performance of DSSC fabricated using unsymmetrical conjugated dendrimers with iodide electrolyte shows higher power conversion efficiency (PCE) than standard LiI based device. Two fold increments are achieved in PCE with first generation unsymmetrical dendrimers compared to their zeroth counterpart. The first generation unsymmetrical dendrimer 8 shows better PCE of 9.037% than all other synthesized dendrimers in the newly fabricated DSSC.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion