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The synthesis and characterization of a family of air-stable primary, secondary, and tertiary phosphines containing all possible combinations of ethylferrocene and ethylruthenocene substituents are reported. Each phosphine was characterized by 1H, 13C, and 31P NMR spectroscopy, IR and UV-vis absorption spectroscopy, mass spectrometry, and elemental analysis. With the exception of primary ethylruthenocene phosphine 8a, all of the title compounds have been studied by single-crystal X-ray crystallography. Ferrocene-containing phosphines showed maximum absorption at wavelengths of ca. 440 nm and qualitatively reversible oxidation waves in their cyclic voltammograms with intensities scaling to the number of ferrocene units present. The average metal-cyclopentadienyl centroid distances observed for ferrocene-containing phosphines were shorter than those of ruthenocene-containing phosphines, which also had maximum absorption wavelengths of ca. 320 nm and underwent irreversible electrochemical oxidation. Phosphines containing both ethylferrocene and ethylruthenocene substituents displayed properties consistent with the presence of both metallocene types.

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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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Novel synthesis of pi-conjugated molecules by cross-metathesis reaction of vinylferrocene with a series of vinylarenes was investigated with a molybdenum-based Schrock catalyst (CHCMe2Ph)Mo(N-2,6-i-Pr2C6H3)[OCMe(C F3)2]2. The cross-metathesis reactions occurred successfully and the cross-metathesis product, i.e., heterodimers, were readily obtained selectively, together with only small amounts of the corresponding self-dimers.

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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 dimesitylphosphinocyclopentene/HB(C6F5)2-derived vicinal trans-1,2-P/B frustrated Lewis pair (FLP) 4 shows no direct phosphane?borane interaction. Toward some reagents it behaves similar to an intermolecular FLP; it cleaves dihydrogen, deprotonates terminal alkynes, and adds to organic carbonyl compounds including CO2. It shows typical intramolecular FLP reaction modes (cooperative 1,1-additions) to mesityl azide, to carbon monoxide, and to NO. The latter reaction yields a persistent P/B FLPNO nitroxide radical, which undergoes H-atom abstraction reactions. The FLP 4 serves as a template for the CO reduction by [HB(C6F5)2] to generate a FLP-eta2-formylborane. The formylborane moiety is removed from the FLP template by reaction with pyridine to yield a genuine pyridine stabilized formylborane that undergoes characteristic borane carbaldehyde reactions (Wittig olefination, imine formation). Most new products were 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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The reaction of Cp?2Zr(OtBu)Me (Cp? = C5H4Me) and [Ph3C][B(C6F 5)4] yields the base-free complex [Cp? 2Zr(OtBu)][B(C6F5)4] (6), which exists as Cp?2Zr(OtBu)(CIR)+ halocarbon adducts in CD2Cl2 or C6D 5Cl solution. Addition of alkenes to 6 in CD2Cl 2 solution at low temperature gives equilibrium mixtures of Cp?2- Zr(OtBu)(alkene)+ (12a-l), 6, and free alkene. The NMR data for 12a-l are consistent with unsymmetrical alkene bonding and polarization of the alkene C=C bond with positive charge buildup at Cint and negative charge buildup at Cterm. These features arise due to the lack of d-pi* back-bonding. Equilibrium constants for alkene coordination to 6 in CD2Cl2 at -89 C, K eq = [12][6]-1[alkene]-1, vary in the order: vinylferrocene (4800 M-1) ? ethylene (7.0) ? alpha-olefins > cis-2-butene (2.2) > trans-2-butene (<0.1). Alkene coordination is inhibited by sterically bulky substituents on the alkene but is greatly enhanced by electron-donating groups and the beta-Si effect. Compounds 12a-l undergo two dynamic processes: reversible alkene decomplexation via associative substitution of a CD2Cl2 molecule, and rapid rotation of the alkene around the metal-(alkene centroid) axis. You can also check out more blogs about1273-86-5 and wish help many people in the next few years. .Formula: C12H3Fe

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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Air-stable primary phosphines were photopolymerized using phosphane-ene chemistry, the phosphorus analogue of the thiol-ene reaction, to fabricate a completely new class of polymer networks. It was demonstrated that the tunable thermal and physical properties accessible using thiol-ene chemistry could also be achieved using an analogous phosphane-ene reaction. At the same time, the presence of the 31P nucleus that is easily observed using NMR spectroscopy allowed the chemical structures of the networks to be directly probed using solid state NMR spectroscopy. Following its incorporation into the network, phosphorus offers the distinct difference and advantage of being able to undergo a diverse array of further derivatization to afford functional materials. For example, the networks were demonstrated to serve as effective oxygen scavengers and to bind transition metals (e.g., Pd). By using the air stable ferrocenyl phosphine (FcCH2CH2)PH2, redox-active networks were produced and these materials could be pyrolyzed to yield magnetic ceramics. Overall, this demonstrates the promise of phosphane-ene chemistry as an alternative to thiol-ene systems for providing functional materials for a diverse range of applications.

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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 method comprises the following steps: dissolving an olefin-based compound and a borane-based compound in a solvent, then adding a zirconium catalyst, reacting the compound in a protective atmosphere at a reaction temperature in 0~150 C a 5min~8h range of up to a reaction temperature in a range of up to a reaction temperature in a range of up to a reaction time and separating to obtain an alkenyl borate compound. The method is simple and convenient to operate, low in cost, high in atom economy of reaction and suitable for industrial production. (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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New ferrocenyl-subtituted compounds containing two different central cores (isocyanurate and 1,3,5-phenylene) and extended by two kinds of branches bearing both vinyl ferrocenyl (1 and 3) and cross-conjugated ferrocenyl-chalcone (2, 4 and 5) as endgroups have been synthetized and characterized both spectroscopically and electrochemically. These molecules have been synthesized in order to investigate the electronic properties imparted by both types of branches when they are connected to the central core. For all compounds, electrochemical studies have showed a simultaneous oxidation of all ferrocene units present in each compound. For all of them, except for compound 2, a chemically reversible oxidation wave on the voltammograms has been observed. In contrast, for compound 2, a chemically irreversible oxidation wave is obtained. Moreover, the vinyl ferrocenyl derivatives have presented a lower redox peak potential with respect to ferrocene standard compound, and the ferrocenyl-chalcone bearing derivatives, in accordance with a change in the electron releasing capability of these endgroups, have been oxidized at a higher potential. Bathochromic shifts of the active transitions in Uv-Vis region have been observed, which are associated to the presence of carbonyl groups in those molecular structures containing it. These results are in agreement with theoretically calculated transition energies, which have been obtained for compounds 1 and 2 using Time Dependent Density Functional Theory (TD-DFT).

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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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Isonicotinyl and pyrazinyl ferrocenyl-derived complexes were prepared using various hydrazides and ferrocenyl aldehydes. Three heterobimetallic complexes were also synthesized from the Schiff base-derived isonicotinyl ferrocene complex using various platinum group metal dimers based on ruthenium, rhodium and iridium. All complexes were evaluated in vitro for antimycobacterial and antiparasitic activity. Against Mycobacterium tuberculosis H37Rv, the platinum group metal complexes showed glycerol-dependent antimycobacterial activity. The antiplasmodial activities against the NF54 chloroquine-sensitive strain of Plasmodium falciparum of some compounds were moderate, while some complexes also showed promising activity against Trichomonas vaginalis. Incorporation of the ferrocenyl-salicylaldimine moiety resulted in enhanced antimicrobial activity compared to the non-ferrocenyl compound in some cases. The bimetallic iridium-ferrocene isonicotinyl complex exhibited superior antitrichomonal activity relative to its organic counterpart, isoniazid. Furthermore, all these compounds, when screened on several normal flora bacteria of humans, showed no effect on the microbiome, emphasizing the selection of these compounds for these pathogens. The promising antimicrobial activities of the complexes thus supports incorporation of ferrocene as part of existing antimicrobial therapies in order to alter their biological activities favorably.

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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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Catalytic enantioselective conjunctive cross-coupling between 9-BBN borate complexes and aryl electrophiles can be accomplished with Ni salts in the presence of a chiral diamine ligand. The reactions furnish chiral 9-BBN derivatives in an enantioselective fashion and these are converted to chiral alcohols and amines, or engaged in other stereospecific C?C bond forming reactions.

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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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In this article, we report the noncovalent linkage of terminal substituted oligo(dimethylsiloxanes) bearing cyclodextrins (CD) as host endgroups and adamantan or ferrocene, respectively, as guest endgroups. Structural characterization was performed by 1H NMR-, IR-, and mass spectroscopy. Electron microscopy studies show significant differences in the surface structure of the individual derivatives. In addition, the ferrocene-terminated di-and poly(dimethylsiloxanes) are distinguished by a red-ox activity and reversibility, which also makes the complexes between the ferrocene- and CD functionalized siloxanes switchable via electrochemical stimuli. The evidence for a successful complexation of the end groups, and thus the successful supramolecular formation of the siloxane strands, was even performed by shift of the protons in the 1H NMR spectra.

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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