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Condensation of 1,11-diacetylferrocene with mono- and disubstituted benzaldehydes in 96% ethanol in the presence of sodium hydroxide has afforded ferrocene-containing dichalcones.

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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 ferrocenyl-substituted mono- (3) and 1,1′-bis-dithiocarboxylic acids (4) have been prepared.These acids react with L2MCl2 (M = Pd, Pt; L = PEt3, PPh3, and 1/2 dppe) in the presence of sodium acetate to give the cis heterodi- and heterotrimetallic complexes cis-L2M (5a: M = Pd, L = PPh3; 5b: M = Pt, L = PPh3; 5c: M = Pt, L = 1/2 dppe) and 2Fe (6a: M = Pd, L = PPh3; 6b: M = Pt, L = PEt3; 6c: M = Pt, L = PPh3; 6d: M = Pt, L = 1/2 dppe).The structures of 5a and 5b have been determined by single-crystal X-ray diffraction. – Key Words: Ferrocene derivatives / 1,1-Ethenedithiolate complexes / Group 10 metal complexes / Heterodimetallic compounds / Heterotrimetallic compounds

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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 double helical architecture generated from a readily prepared ferrocenyl-containing bisthiosemicarbazone ligand is described together with its application to the self-assembly of novel supramolecular hydrogen-bonding cavities.

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The d4 halide complexes [MX(CO)(eta-RCCR)Tp?] {X = F, Cl, Br or I; R = Me or Ph; M = Mo or W; Tp? = hydrotris(3,5- dimethylpyrazolyl)borate} undergo one-electron oxidation to the d3 monocations [MX(CO)(eta-RCCR)Tp?]+, isolable for M = W, R = Me. X-Ray structural studies on the redox pairs [WX(CO)(eta-MeCCMe)Tp?] z (X = Cl and Br, z = 0 and 1), the ESR spectra of the cations [WX(CO)(eta-RCCR)Tp?]+ (X = F, Cl, Br or I; R = Me or Ph), and DFT calculations on [WX(CO)(eta-MeCCMe)Tp?]z (X = F, Cl, Br and I; z = 0 and 1) are consistent with electron removal from a HOMO (of the d4 complexes) which is pi-antibonding with respect to the W-X bond, pi-bonding with respect to the W-C(O) bond, and delta-bonding with respect to the W-Calkyne bonds. The dependence of both oxidation potential and nu(CO) for [MX(CO)(eta-RCCR)Tp?] shows an inverse halide order which is consistent with an ionic component to the M-X bond; the small size of fluorine and its closeness to the metal centre leads to the highest energy HOMO and the lowest oxidation potential. In the cations [MX(CO)(eta-RCCR)Tp?] + electronegativity effects become more important, leading to a conventional order for Cl, Br and I. However, high M-F pi-donation is still facilitated by the short M-F distance. The Royal Society of Chemistry.

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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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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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Condensation of diacetylferrocene with cyclohexanone, alkyl- or phenyl-cyclohexanones and cycloheptanone carried out in DMSO in the presence of KOH afforded 3-spiro<5>ferrocenophane-1,5-diones.Cyclopentanone and cyclooctanone failed to give the spiroferrocenophanediones.The mechanism of the reaction, its limitations and side products are discussed.Detailed analysis of the 1H NMR and 13C NMR spectra revealed an influence of the cyclohexane ring substituents on the flexibility of the spiroferrocenophanedione bridge.Fragmentation of the product molecules upon electron impact is also described.

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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 keto-phosphines (L1), <(Ph2PCH2C(O)(eta5-C5H4))2Fe> (L2) and <(Ph2PCH2C(O)(eta5-C5H4)C(O)CH3)> (L3) were respectively prepared by the reaction of Ph2PCl with the lithium enolates derived from acetylferrocene for L1, and 1,1′-bis(acetyl)ferrocene for L2 and L3.Ligand L1 crystallizes in the space group P1 with a 8.526(2), b 10.915(3), c 12.822(3) Angstroem, alpha 63.75(2), beta 69.04(2), gamma 70.77(2) deg, V 978.4 Angstroem3 and Z 2.The structure was solved and refined to R=0.034 and RW=0.042.The C5-rings are eclipsed (3.2 deg) and the plane of the keto group forms a dihedral angle of 13.1 deg with the C5H4 plane.In the complexes cis- and trans- (cis-1 and trans-1), <(o-C6H4CH2NMe2)PdClL1> (2), cis- (3), and (4) the phosphine ligand(s) behave as P-monodentate(s).The structure of trans-1 has been determined by X-ray diffraction at -145 deg C.The complex crystallizes in the monoclinic space group P21/c with a 10.622(7), b 12.647(7), c 15.59(1) Angstroem, beta 103.20(6) deg, V 2039 Angstroem3 and Z=2.The structure was solved and refined to R=0.037 and RW=0.053.The palladium atom lies on a centre of symmetry and the Pd-P and Pd-Cl bond lengths are respectively 2.314(1) and 2.287(1) Angstroem.The C5-rings of each ligand are slightly staggered (10.5 deg) and, as for L1, each keto group is almost parallel to the C5H4 plane (dihedral angle 8.9 deg).For the complex BF4, NMR and IR solution spectroscopy has shown that there is a dynamic exchange between chelating and P-monodentate L1.The possibility of using L2 as a binucleating ligand was demonstrated by the preparation of the trinuclear complex <((C10H8N)PdCl)2(mu-L2-P,P')> (6).The enolato complexes cis- (M=Pd (7), M=Pt (8)), and <(o-C6H4CH2NMe2)Pd(Ph2PCH=C(O)(eta5-C5H4)Fe(eta5-C5H5))> (9) were prepared in high yield by the reaction of NaH with complexes 1, 3, and 2, respectively.Complex 9 reacts with dimethylacetylenedicarboxylate to yield the alkenyl complex <(o-C6H4CH2NMe2)Pd(Ph2PCH(MeO2CC=CCO2Me))> (10), resulting from carbon-carbon coupling between the P bound enolate-carbon atom and the alkyne.All the complexes were characterized by elemental analysis, and 1H and 31P(1H) NMR and IR spectroscopy.

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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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Treatment of 1,1?-diacetylferrocene (10) with excess piperidine and a stoichiometric amount of TiCl4 in pentane leads to CC-coupling of the two functional groups at the ferrocene framework. This enamine condensation reaction leads to the formation of the 1,3-connected dienamine-bridged [3]ferrocenophane system 13a. Complex 13a was characterised by X-ray crystal structure analysis. The analogous TiCl4-mediated coupling and condensation reactions of 10 with morpholine, pyrrolidine or methyl-isopropylamine yield the corresponding substituted [3]ferrocenophane systems 13b-d.

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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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New ferrocene naphthyridine derivatives were successfully synthesized. The di-substituted ferrocene derivative FecDN behaves as a selective visual chemosensor for mercury ions, exhibiting a rapid and clearly visible precipitation with good selectivity (precipitation) and sensitivity (0.01 muM). The interaction of the ferrocene derivatives and metal ions was investigated by ultraviolet-visible spectroscopy (UV-vis), electrochemical methods, 1H NMR, as well as infrared (IR), and energy dispersive X-ray spectroscopy (EDX). The application of FecDN in the detection and removal of mercury ions is very simple, rapid, and intuitive.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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New tetrakis-and hexakis(1H-pyrrole-2-carbaldehyde) anion receptors are described. The anion binding properties of these receptors were studied in organic media and in the solid state. The receptors displayed good affinity for the dihydrogenphosphate and pyrophosphate anions (as the tetrabutylammonium salts) in chloroform even in the presence of a polar protic solvent, methanol. Solution phase spectroscopic analyses proved consistent with the binding mode seen in single crystal structural studies of the dihydrogenphosphate and pyrophosphate complexes and provided support for the contention that these receptors undergo conformational reorganization in order to accommodate the bound oxoanions both in chloroform solution and in the solid state.

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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