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A facile, highly stereo- and regioselective hydrometalation of alkynes generating alkenylmetal complex is disclosed for the first time from a reaction of alkyne, carboxylic acid, and a zerovalent group 10 transition metal complex M(PEt3)4 (M = Ni, Pd, Pt). A mechanistic study showed that the hydrometalation does not proceed via the reaction of alkyne with a hydridometal generated by the protonation of a carboxylic acid with Pt(PEt 3)4, but proceeds via a reaction of an alkyne coordinate metal complex with the acid. This finding clarifies the long proposed reaction mechanism that operates via the generation of an alkenylpalladium intermediate and subsequent transformation of this complex in a variety of reactions catalyzed by a combination of Bronsted acid and Pd(0) complex. This finding also leads to the disclosure of an unprecedented reduction of alkynes with formic acid that can selectively produce cis-, trans-alkenes and alkanes by slightly tuning the conditions.

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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 electrochemical systems imperfect thermostating inevitably leads to the presence of bulk convective flows. As recognised by Nernst [Z. Phys. Chem., 1904, 52] damping of these bulk convective flows next to a solid surface, or at the electrode, leads to diffusional mass transport predominating locally. This work questions the exclusivity of diffusional transport and provides hitherto unexplored physical insights into how thermally induced flows in bulk solution can, on both macro- and microelectrodes, influence a voltammetric measurement. Imperfect thermostating results in flows in the bulk solution which are predicted and here expeimentally shown to be of the order of 100 mum s-1. Here we show that even in the absence of natural convective flows induced by the electrochemical reaction itself, this thermally induced bulk convection can significantly affect the voltammetric response. First, evaporative losses from an open electrochemical cell can be sufficient to produce convective flows that can alter the electrochemical response. Second, electrodes with various sizes and geometries have been investigated and experimental results evidence that the sensitivity of an electrode to these flows in bulk solution is to a large extent controlled by the size of the surrounding non-conductive supporting substrate used to insulate parts of the electrode.

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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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X-Ray structural and EPR spectroscopic studies of the redox-related pairs [WX(CO)(MeC=CMe)Tp’](z) (X = F, Cl, Br and I; z = 0 and 1) [Tp’ = hydrotris(3,5-dimethylpyrazolyl)borate] are consistent with the HOMO of the d4 (z = 0) species being pi-bonding with respect to the W-CO bond, pi- antibonding with respect to the W-X bond, and delta-bonding with respect to the W-alkyne bond.

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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 synthesis of aromatic dicarboxaldehydes is described along with their reactivity in the [3 + 3] cyclocondensation reaction with (1R,2A)- diaminocyclohexane to give trianglimine macrocycles. In particular, the scope and limitation of the reaction with regard to complete control of the cavity size of the macrocycles is discussed producing a total of 11 macrocycles with different cavity sizes ranging from 9 to 23 A. The Royal Society of Chemistry 2005.

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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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Chemical engineers ensure the efficiency and safety of chemical processes, adapt the chemical make-up of products to meet environmental or economic needs, and apply new technologies to improve existing processes. SDS of cas: 1273-86-5. Catalysts allow a reaction to proceed via a pathway that has a lower activation energy than the uncatalyzed reaction. Introducing a new discovery about 1273-86-5, Name is Ferrocenemethanol

We report a synthetic nickel complex containing proton relays, [Ni(P Ph2NC6H4OH2)2](BF4) 2 (PPh2NC6H4OH2 = 1,5-bis(p-hydroxyphenyl)-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclo-octane), that catalyzes the production of H2 in aqueous acetonitrile with turnover frequencies of 750-170000 s-1 at experimentally determined overpotentials of 310-470 mV.

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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 relates to a kind of ferrocene naphthyridine derivatives and its preparation and use. The design of the invention the synthetic model ferrocene naphthyridine derivatives of high productivity, cost, can effectively identify and absorb the Hg in the liquid2 + , And Cu2 + There are also identification function, in purifying the environment have a wide range of application prospect. (by machine translation)

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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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We describe the synthesis, binding, and electrochemical properties of ferrocene-conjugated oligonucleotides (Fc-oligos). The key step for the preparation of Fc-oligos contains the coupling of vinylferrocene to 5-iododeoxyuridine via Heck reaction. The Fc-conjugated deoxyuridine phosphoramidite was used in the Fc-oligonucleotide synthesis. We show that thiol-modified Fc-oligos deposited onto gold electrodes possess potential ability in electrochemical detection of DNA base mismatch.

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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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Title full: Synthesis and characterization of 1,1?-bis[(N-methyl-N-phenyl)aminomethyl(ethyl)]ferrocenes. Crystal structures of [Fe{(eta5-C5H4)-C(C6H 5){double bond, long}N-CH2C6H4CH3-4} 2] and 2[Fe{(eta5-C5H4)-CH2N (CH3)-C6H4OCH3-4}2] · 1/4H2O. Direct or catalytic condensation of diacylferrocenes (acyl = formyl, acetyl, and benzoyl) and anilines or benzylamines with titanium tetrachloride as a catalyst resulted in the corresponding diimines 1-3, respectively. Reduction of these imines with sodium borohydride or lithium aluminum hydride/aluminum chloride in THF yielded 1,1?-bis[(N-phenyl)aminomethyl(ethyl)]ferrocenes (4, 5) and 1,1?-bis[(N-benzyl)aminobenzyl]ferrocenes (6), respectively. Reductive methylation of 4-6 with aqueous formaldehyde, cyanoborohydride and acetic acid only afforded 1,1?-bis[(N-methyl-N-phenyl)aminomethyl(ethyl)]ferrocenes (7, 8). 1,1?-Bis[{(N-methyl-N-benzyl)amino}benzyl]ferrocenes (9) were not obtained, probably due to their debenzylation under the acidic conditions. The molecular structures of 3g and 7a were determined by single crystal X-ray analysis.

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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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A photoinduced copper-catalyzed three-component reaction involving carbohalide, alkene and amine has been developed, leading to valuable fluoroalkyl-containing amines. A sole inexpensive CuCl is used as the photo- and coupling catalyst. A broad array of substrates are capable coupling partners. The diverse method is compatible with a broad range of functional groups and can be further applied to the late-stage functionalization of bioactive pharmaceuticals.

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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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Herein are reported the synthesis and the full characterization of three new ferrocenyl monomers, namely 2-(ferrocenylmethoxy)ethyl methacrylate (FMOEMA), 3-(ferrocenylmethoxy)propyl methacrylate (FMOPMA) and 4-(ferrocenylmethoxy)butyl methacrylate (FMOBMA), synthesized from ferrocenemethanol. Homopolymers were prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization in toluene at 70C using 2-cyanoprop-2-yl-dithiobenzoate (CPDB) as a chain transfer agent. Polymerization kinetics were compared to those of the well-known 1-ferrocenylmethyl methacrylate (FMMA). The ferrocenyl containing monomers with alkoxy linkers were found to be as reactive as FMMA in RAFT polymerization. Polymers with controlled molar masses with dispersities lower than 1.5 were obtained. The chemical structures of the monomers and polymers were fully characterized by NMR and size exclusion chromatography. Glass transition temperatures of these methacrylic polymers ranged from 36C to 2C when controlling the length of the alkoxy linker between the ferrocene unit and the backbone. The electrochemical properties of the monomers and the homopolymers were demonstrated using cyclic voltammetry.

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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