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Protonation of p-xylylaminomethylferrocene (1) and n- hexylaminomethylferrocene (2) by HCl and NH4PF6 forms the ferrocenylmethyl(alkyl)ammonium salt. Inclusion of the compounds by dibenzo[24]crown-8 (DB24C8) produces [2]pseudorotaxanes, [(DB24C8)(1-H)] +(PF6) and [(DB24C8)(2-H)]+(PF6), respectively. X-ray diffraction of the former product indicates an interlocked structure composed of the axis and the macrocyclic molecule. Intermolecular N-H…O and C-H…O interactions and stacking of the aromatic planes are observed. [(DB24C8)(1-H)]+(PF6), in the solid state, is characterized by IR spectroscopy and elemental analyses. A similar reaction of 1,1?-bis(p-xylylaminomethyl)ferrocene (3) forms a mixture of [2] and [3]pseudorotaxanes, [(DB24C8)(3-H2)]2+(PF 6)2 and [(DB24C8)2(3-H2)] 2+(PF6)2. The latter product having two DB24C8 molecules is isolated and characterized by X-ray crystallography. Formation of these pseudorotaxanes in a CD3CN solution is evidenced by 1H NMR and mass spectrometry. Electrochemical oxidation of 1-3 at 0.4 V (vs Ag+/Ag) in the presence of TEMPOH (1-hydroxy-2,2,6,6- tetramethylpiperidine) and DB24C8 affords the corresponding pseudorotaxanes. The ESR spectrum of the reaction mixture indicates the formation of a TEMPO radical in high yield. Details of the conversion of the dialkylamino group of the ligand to the dialkylammonium group are investigated by using a flow electrolysis method linked to spectroscopic measurements. The proposed mechanism for the reaction involves the ferrocenium species, formed by initial oxidation, which undergoes electron transfer from nitrogen to the Fe(III) center, producing a cation radical at the nitrogen. Transfer of hydrogen from TEMPOH to the cation radical and inclusion of the resulting dialkylammonium species by DB24C8 yields the pseudorotaxanes.

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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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Several new ferrocene-functionalised porphyrins and a ruthenocene-functionalised porphyrin have been synthesized and studied using electrochemistry, electronic absorbance and resonance Raman spectroelectrochemical techniques. The porphyrin and ferrocene are observed to have limited effect on each other with the properties of the porphyrin dominating the spectroscopy of these molecules. The Royal Society of Chemistry 1999.

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The preparation, electrochemical, electronic, and cation sensing properties of an indole-ferrocene-indole triad, are presented. A salient feature of this new structural motif is that the redox-active organometallic fragment is linked to the indole rings by unsaturated nitrogen functionalities. Triad 4 behaves as a highly selective dual-redox and chromogenic chemosensor molecule for Hg 2+ cations: the oxidation redox peak is anodically shifted (DeltaE1/2 = 210 mV), and the low energy band of the absorption spectrum is red-shifted (Deltalambda = 120 mm), upon complexation with this metal cation. This change in the absorption spectrum is accompanied by a dramatic colour change from orange to green which allows the potential for “naked eye” detection. 1H NMR as well as DFT calculations have been carried out to get information about the molecular sites which are involved in bonding.

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

 

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Condensation reactions of the phosphodihydrazide XP(Ph)(NMeNH2)2 (X = O 1a, S 1b) with ferrocene-1,1′-dicarboxaldehyde 2 afford in good yield the first examples of phosphorus ferrocenyl macrocycles Fe2Fe (X = O 3a, S 3b) and 3b can be converted to the new compounds Fe2Fe 5 and 2Fe>2 6 by reaction with, respectively, LAH and CF3SO3Me; 5 represents a novel prototype of an anion receptor which electrochemically recognises the H2PO4-, HSO4- and Cl- anions.

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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 reductive deoxygenation of alpha-ferrocenyl aldehydes, ketones, alcohols, and carboxylic acid into the corresponding alkylferrocenes is accomplished solely by borane-dimethyl sulfide (BMS) in the absence of any Lewis acid catalyst. This is the first example of such reactivity of BMS. The present method allows the synthesis of alkylferrocenes including those bearing terminally functionalized pendant chains.

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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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Meso-substituted corroles bearing directly linked ferrocene unit have been synthesized for the first time. Among various methods studied, only the condensation of pentafluorophenyldipyrromethane with a formylferrocene led to this type of product. A triad containing corrole and porphyrin bridged with ferrocene has been obtained by a convergent approach. Bilanes were used as crucial substrates in the porphyrin-forming step. For the first time it was shown that H2O-MeOH-HCl conditions are suitable for preparation of various 10-(formylaryl)corroles via the direct condensation of aromatic dialdehydes with dipyrromethanes. Electrochemical studies of 10-ferrocenyl-5,15-bis(pentafluorophenyl)corrole support the possibility of intramolecular electron transfer from the corrole to the ferrocene system after the electrode oxidation of the ferrocene to a ferrocenium cation. We have studied the structure of 1-(corrolyl)-1?-(porphyrinyl)ferrocene by 1H NMR and UV-Vis. NMR spectra show that this compound has more conformational freedom than analogous, previously studied bis- porphyrinylferrocenes. Absorption spectra suggest the lack of strong electronic interaction between ferrocene and porphyrinoids for dyads and significant conjugation for the triad. The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.

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Herein is described the synthesis of (+)-camphor derivatives containing sulfonamide groups, ferrocenylmethylidene or arylidene moieties. The obtained derivatives were tested against seven human cancer cells lines, namely BV-173, K-256a, NB-4, A549, H1299, MCF-7, and MDA-MB231, and two normal human cell lines, HEK293 and HUVEC, in order to determine their activity against malignant cells. Some of them exhibit IC50 values below 10 muM in at least one of the cancer cell lines. Ferrocenylmethylidene ketone 16 can be outlined as the most potent and selective in the current study (IC50 for cancer cells-up to 4.0 muM; IC50 for HEK293 and HUVEC-68 and 69 muM, respectively). There is a clear trend showing that the presence of a conjugated ferrocenylmethylidene group is essential for the cytotoxicity, however different sulfonamide substituents and derivatization of the carbonyl group can modify the activity. Thus, this class of compounds could have good prospects for further structural optimisation.

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Grinding of 1,1?-ferrocenedicarboxaldehyde with a 2.2 molar equivalent of an aromatic amine in a solvent-free environment provided excellent yields of 1,1?-ferrocenyldiimines. After mixing the aldehyde and amines, a gum or melt formed which eventually solidified to the product. An analytically pure sample of the product was obtained by cold recrystallization. Grinding of ferrocenecarboxaldehyde and 4-substituted phenylacetonitriles under solvent-free conditions provided good yields of the corresponding ferrocenylacrylonitriles. The yield in this reaction was very low when the substituent group para to the acetonitrile group was electron-donating.

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Exclusively planar chirality is exhibited by the ferrocenes obtained in a highly enantioselective synthesis in which a chiral aminoamide acts as a temporary protecting/directing group. This method was used to obtain an enantiomerically pure tetrasubstituted ferrocene, which was transformed into the first C2-symmetric disubstituted ferrocenophane [Eq. (1)].

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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Ferrocene-bridged trisporphyrin (2) was synthesized by two-steps condensation of corresponding aldehydes and dipyrromethanes, and its self-assembling behavior based on the complementary coordination motif of imidazolylporphyrinatozinc(II) was investigated in conjunction with hinge-like flexibility given by freely rotating cyclopentadienyl rings of ferrocene connector. Ferrocene-bridged trisporphyrin (2) spontaneously and exclusively generated the dimeric ring (7) upon simple zinc(II) insertion, indicating that the freely rotating hinge connector favored the smallest ring formation. Taking advantage of the unique hinge-like flexibility of ferrocene, we attempted to transform the dimer ring into a mixture of porphyrin macrocycles by reorganizing the structure cleaved once by pyridine. A series of porphyrin macrocycles from trimer to decamer can be separated into its components by preparative gel permeation chromatograms. Macrocycles obtained are kept stable in the absence of coordinating solvents. On the other hand, they were easily transformed to the dimer ring in the presence of coordinating solvents such as methanol, showing that the transformation is completely reversible and can be controlled by the choice of the solvent system. A series of porphyrin macrocycles was confirmed via covalent linking of each complementary coordination dimer pair by metathesis reaction in the presence of Grubbs’s catalyst. The coordination behavior of the bidentate ligands with different spacer lengths toward the dimer ring revealed that only the bidentate ligand (15) with a spacer length that matched the facing central porphyrins was selectively accommodated inside the ring. Coordination assembled flexible rings with tunable cavities and multiple coordination sites will be used as versatile hosts for a wide variety of guest molecules.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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