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This paper describes the orbital configuration which provides a basis for the understanding of the electronic structure and spectroscopic properties of 17e and 18e FcC2R and FcC4R dyads, where R is H, 1-naphthyl, 9-anthryl, 3-pyrenyl, perylenyl. DFT calculations show that destabilisation of the ferrocenyl pi orbitals upon binding a C{triple bond, long}CR group to a Cp ring leads to the metal-based a1 orbital dropping below the e1-a so that the frontier orbital configuration is (e2? -a, pi)2 (e2? -b,metal)2 (e1? -a, pi)2, (a1, metal)2. The contribution of the aryl group to the pi e2-a and e1-a orbitals varies with the annelation of the ring. The LUMO is aryl based. The calculations are consistent with the spectroscopic data for the 18e species. Oxidation to the 17e cations does not change the orbital configuration but the orbital energies are lowered by the positive charge centred on the Fe. A strongly solvatochromic transition in the near-IR, a signature for the 17e cations, is best described as an LMCT transition but the contribution of C2R and C4R to the donor and acceptor levels depends on the ionization energy of the aryl pi orbital. LMCT energies decrease from FcC2R to FcC4R dyads.

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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 new method for substitution of a vinylic hydrogen with an alkyl group (a Mizoroki-Heck type transformation) was developed by a titanocene catalyst in the presence of nBuMgCl. This reaction could proceed regio- and stereoselectively under mild conditions to afford E-olefins using primary and secondary alkyl halides. The reactions of aliphatic alkenes, e.g., 1-octene and internal alkenes, were sluggish. When t-alkyl halides were employed, alkylative dimerization of alkenes proceeded exclusively to give symmetrical vic-diarylalkanes. These reactions involved addition of alkyl radicals to arylalkenes to form benzyl radicals as a carbon-carbon bond-forming step. Dimerization of thus formed benzyl radicals afforded symmetrical alkanes and beta-hydrogen elimination from benzyltitanocene intermediates gave alkylated alkenes. A possibility that titanocene activates alkenes as radical accepters was also proposed.

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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 functional group exchange reaction between allylamines and alkenes via nickel-catalyzed C – C bond cleavage and formation was developed. This reaction provides a novel protocol, which does not require the use of unstable imine substrates, for the synthesis of allylamines, which are widely used in the production of fine chemicals, pharmaceuticals, and agrochemicals.

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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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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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The reaction of tris(3-iodopentane-2,4-dionato)cobalt(III) with vinylferrocene in the presence of triphenylphosphine and a catalytic amount of PdII produced two structural isomers.The characterisation of these isomers, 2- and 3-ferrocenyl-4-acetyl-2,3-dihydro-5-methylfuran <(B) and (C), respectively> is described.Their structures have been determined by single-crystal X-ray diffractometry: (B) is orthorhombic, space group Pbca with a=9.821(2), b=10.414(4), c=27.761(6) Angstroem, final R=0.031, R’=0.050 for 1706 reflections; (C) is monoclinic, space group is P21/c with a=9.692(1), b=7.678(5), c=19.082(3) Angstroem, final R=0.031, R’=0.048 for 1641 reflections.

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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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Ethynylferrocenyl derivatives of 2,7-acridine (1, 2), 9-N-acridone (4), and 2-anthraquinone (6) are described. (Z)-10-(2-iodo-1-ethenylferrocene)-9(10H)-acridinone (3), an intermediate in the formation of 4, N-Fc(CH2)n-acridone (5; n = 8, 11), 1-Fc-anthraquinone (7), and (E)-(2-FcC=C)-anthraquinone (8) were also investigated. The X-ray structures of 3 and 6 were determined. B3LYP calculations, UV/vis spectroelectrochemistry, cyclic voltammetry, and ESR spectra were used to probe the ground and excited states of both the neutral and oxidized compounds. Emission is observed from oxidized, but not neutral, 4 and 6; however, 1, 2, and 8 are fluorescent. Surprisingly, emission is reduced upon oxidation of 2 and 8, which appears to correlate with the greater distortion in the excited compared to ground states.

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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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57Fe NMR spectra of 20 ferrocene derivatives with natural abundance of 57Fe have been recorded by the conventional pulse Fourier transform technique using ferrocene as internal standard for the chemical shifts.Shift contributions of the substituents are discussed qualitatively.

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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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A series of novel 2-ferrocenyl-3,4-dihydropyrans were synthesized in good to excellent yields through three-component reaction of vinylferrocene, 1,3-dicarbonyl compound and formaldehyde near room temperature under catalyst-free conditions. The obtained ferrocenyl dihydropyrans can also react readily with indole in the presence of alum, providing a ring-opening product in high yield, and this result opens an effective way to access a new class of complex ferrocenyl derivatives.

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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 reaction of alpha-hydroxyferrocenylalkyl derivatives and vinylferrocene with 1,5-disubstituted tetrazoles in methylene chloride-aqueous acid HX (X = BF4, ClO4) two-phase systems gives a mixture of 1,3,5- and 1,4,5-trisubstituted tetrazolium salts, the fraction of the 1,3,5-isomers prevailing. The synthesized salts are readily dealkylated under the action of bases to give the above starting compounds. Heating of 3(4)-(ferrocenylmethylene)-1,5-pentamethylenetetrazolium and 3(4)-(ferrocenylmethylene)-2-methyl-1-phenyltetrazolium tetrafluoroborates in anhydrous methanol or ethanol in the presence of catalytic amounts of alkali gives rise to ferrocenylcarbinol ethers. Other nuclephiles (pyridine, triphenylphosphine, sodium thiocyanate, sodium p-toluenesulfinate, dibenzoylmethane) also react with the above tetrazolium salts, forming ferrocenylmethylation products. Heating of equimolar amounts of 3(4)-(ferrocenylmethylene)-1,5-pentamethylenetetrazolium or 3(4)- (ferrocenylmethylene)-2-methyl-1-phenyltetrazolium perchlorates with mercury(II) perchlorates in anhydrous ethanol results in mercuration of the starting tetrazolium salts, involving hydrogen substitution in the methylene or methyl groups bound to tetrazolium carbon atoms. The condensation of the same salts with p-N,N-(dimethylamino)nitrosobenzene, leading to azomethine formation, occurs under similar 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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A base-free nickel-catalyzed hydroboration of unreactive simple alkenes with bis(pinacolato)diboron using methanol as the hydride source under mild conditions has been developed. Methanol as the solvent proved to be critical for the base-free conditions and high reactivity. A series of linear alkylboronates were synthesized in moderate to excellent yields with high regioselectivity.

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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