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Synthesis and metallation of ferrocenylimines derived from ligating diaminoheteroarenes

A regioisomeric mixture of 1,1?-didodecylferrocenedicarbaldehydes 3 was prepared from the reaction of a regioisomeric mixture of 1,1?-didodecyldilithioferrocenes and dimethylformamide. Three ligating heteroaromatics were synthesized each containing two amino substituents: 5,5?-diamino-2,2?-bipyridine and 5,5?-diamino-2,2? : 6?,2?-terpyridine were prepared from appropriate dinitro compounds by reduction with palladium on charcoal-hydrazine hydrate. The reaction of 2-cyano-5-nitropyridine and hydrazine hydrate gave an isolable amidine derivative and this was transformed with hydrazine in a separate reaction under more forcing conditions into 3,6-bis(5-amino-2-pyridyl)-1,2-dihydro-1,2,4,5-tetrazine. The latter was converted into the tetrazine by oxidation (2,3-dichlpro-5,6-dicyano-1,4-benzoquinone) and then trifluoroacetylated [(CF3CO)2O] to give the bis(trifluoroacetylamino) derivative. Diels-Alder reaction of the latter with dodec-1-yne afforded 4-n-decyl-3,6-bis[5-(trifluoroacetylamino)-2-pyridyl]pyridazine which was deprotected (K2CO3) to give the corresponding diamine. Bis(ferrocenyl) Schiff bases were prepared from ferrocenecarbaldehyde and the appropriate diamine in either uncatalysed or acid-catalysed condensations. Tetracarbonylmolybdenum complexes were prepared by treating the appropriate diamines with molybdenum hexacarbonyl. Reaction of one of these complexes with ferrocenecarbaldehyde gave a heterobimetallic complex.

Synthesis and metallation of ferrocenylimines derived from ligating diaminoheteroarenes

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Electric Literature of 1271-48-3, Catalysts function by providing an alternate reaction mechanism that has a lower activation energy than would be found in the absence of the catalyst. In some cases, the catalyzed mechanism may include additional steps.In a article, 1271-48-3, molcular formula is C12H10FeO2, introducing its new discovery.

Structural influences on the electrochemistry of 1,10-di(hydroxyalkyl) ferrocenes. Structure of [Fe{h5-C5H4eCH(OH)e(CH2)3OH}2]

Abstract A series of 1,1′-di(hydroxyalkyl)ferrocenes, [Fc'{(CH 2)nOH}2], with n = 1 (1), 2 (2), 3 (3) and 4 (4) and Fc’ = Fe(eta5-C5H4)2, was synthesized. The electrochemistry of the di(hydroxyalkyl)ferrocenes was studied by cyclic voltammetry in CH2Cl2/0.1 M [N nBu4][PF6] utilizing a glassy carbon working electrode. The ferrocenyl group showed reversible electrochemistry with the formal reduction potential, Eo’ , inversely proportional to alkyl chain length and approximately 59 mV smaller than those of the corresponding mono(hydroxyalkyl)ferrocenes derivatives [Fc(CH2)mOH] with m = 1 (1m), 2 (2m), 3 (3m), and 4 (4m) and Fc = Fe(eta5-C 5H5)(eta5-C5H4 -). The tetraalcohol [Fc'{CH(OH)(CH2)3OH} 2], 5, possessing four OH functionalities, two in the terminal positions and two more, one on each of the two alpha-C relative to the ferrocenyl (Fc’ for dialcohols or Fc for monosubstituted derivatives) group, was isolated as a side product during the synthesis of 4. The formal reduction potential of 5 was Eo’ = -24 mV vs. FcH/FcH+ and closely approached Eo’ of [FcCH(OH)CH3] (Eo’ = -11 mV), [Fc'{CH(OH)CH3}2] (-21 mV) and 1 (0.00 mV vs. FcH/ FcH+). The single crystal X-ray structure of the tetraalcohol 5 (Z = 8, orthorhombic, space group Pbca) was also solved.

Structural influences on the electrochemistry of 1,10-di(hydroxyalkyl) ferrocenes. Structure of [Fe{h5-C5H4eCH(OH)e(CH2)3OH}2]

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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Synthesis, structure and properties of new ferrocene-containing compounds

The potential use of (aminomethyl)ferrocene and 1,1? -di(aminomethyl)ferrocene as precursor for Schiff base chemistry has been tested. (Aminomethyl)ferrocene reacts with 3,3? -(3-oxapentane-1,5-diyldioxy)bis(2-hydroxybenzaldehyde) to give the [2+1] diiminic ligand 8. 8 reacts with LaCl3 and Ni(CH3COO) 2 giving the corresponding complexes 9 and 10. 1,1? -Di(aminomethyl)ferrocene was prepared by conversion of 1,1? -di(formyl)ferrocene into 1,1?-di(formyl)ferrocene oxime, followed by reduction of the oxime with LiAlH4. Easy degradation of 1,1?-di(aminomethyl)ferrocene prevented its use as aminic precursor for the synthesis of Schiff base ligands. Isomerization occurred about the carbon-nitrogen double bonds of 1,1?-di(formyl)ferrocene oxime giving rise to three isomers. The X-ray analysis has shown that in the 5a complex three independent molecules having different conformation are present.

Synthesis, structure and properties of new ferrocene-containing compounds

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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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Synthesis, reactivity and spectroscopy of ferrocene-functionalised porphyrins, with a conjugated connection between the ferrocene and the porphyrin core

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.

Synthesis, reactivity and spectroscopy of ferrocene-functionalised porphyrins, with a conjugated connection between the ferrocene and the porphyrin core

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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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Ditopic redox-active polyferrocenyl zinc(II) dithiocarbamate macrocyclic receptors: Synthesis, coordination and electrochemical recognition properties

The synthesis of a range of ditopic polyferrocenyl zinc(II) dithiocarbamate macrocyclic receptors containing ferrocene groups on the macrocycle’s periphery and/or as part of the cyclic cavity is reported. The assemblies have been characterised by a range of spectroscopic techniques, electrochemical studies and in two cases by X-ray structure determination. The ability of these host systems to bind and sense electrochemically anionic guest species, isonicotinate and benzoate, and neutral 4-picoline guest was examined by 1H NMR and cyclic voltammetric titration studies. The strongest association was found between the isonicotinate anion and a dinuclear zinc(II) receptor whose macrocyclic cavity is of complementary size to complex this bidentate guest species in a cooperative manner. Cyclic voltammetric studies demonstrated that all receptors can electrochemically sense the binding of isonicotinate and benzoate via significant cathodic perturbations of the respective ferrocene redox couple. The Royal Society of Chemistry 2005.

Ditopic redox-active polyferrocenyl zinc(II) dithiocarbamate macrocyclic receptors: Synthesis, coordination and electrochemical recognition properties

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A new tris(ferrocenylamine) ditertiary phosphine: Synthesis and co-ordination studies

The new tris(ferrocenylamine) ditertiary phosphine 1,1?-{FcCH2N(CH2PPh2)CH2(eta5-C5H4)}2Fe [Fc = (eta5-C5H5)Fe(eta5-C5H4)] has been prepared along with two coordination complexes. All compounds have been characterised by a combination of spectroscopic and analytical methods. The single crystal X-ray structure of the pentametallic Ru2Fe3 complex 5 has been determined.

A new tris(ferrocenylamine) ditertiary phosphine: Synthesis and co-ordination studies

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A double-a silicon oxygen radical three carbon ester ferrocene monomer and its preparation method (by machine translation)

The invention relates to a double-a silicon oxygen radical three carbon ester ferrocene monomer and its preparation method. Double-a silicon oxygen radical three carbon ester ferrocene monomer the chemical structural formula of I shown in the following: the double a silicon oxygen radical three carbon ester ferrocene preparation method of the monomer is 1, 1′ – double-aldehyde ferrocene and 1 – methoxy – 1 – (trimethyl siloxy) – 2 – methyl – 1 – propene in the final ether complex as catalyst under the conditions of the double-a silicon oxygen radical three carbon ester by the reaction of the ferrocene monomer. The invention preparation of double-a silicon oxygen radical three carbon ester ferrocene monomer can be applied to the preparation of an electrically conductive material. (by machine translation)

A double-a silicon oxygen radical three carbon ester ferrocene monomer and its preparation method (by machine translation)

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Self-assembly via (N?I) non-covalent bonds between 1,4-diiodo-tetrafluoro-benzene and a tetra-imino ferrocenophane

The tetra-imino ferrocenophane (1) was cocrystallized with 1,4-diiodo-tetrafluoro-benzene (TFDIB). In the resulting compound 2, two of the four ferrocenophane nitrogens show interactions with the iodine atoms of TFDIB leading to a polymeric structure with extended linear alternating electron donor (1) and acceptor (TFDIB) molecule chains. For the first time, imino nitrogens are involved in this type of halogen bonding. The N?I non-covalent bonds (N?I distances 2.879(5) and 2.896(5)A; N?I-C angles 171.1(2) and 178.1(2)) are the directing interactions responsible for the observed self-assembly. The ferrocene fragments of the macrocycle are in an almost perpendicular conformation. Moessbauer spectroscopy indicates the sole presence of low spin iron (II). The temperature dependence of the magnetic susceptibility is corresponding to a quasi-diamagnetic compound.

Self-assembly via (N?I) non-covalent bonds between 1,4-diiodo-tetrafluoro-benzene and a tetra-imino ferrocenophane

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Ferrocenyl-cymantrenyl hetero-bimetallic chalcones: Synthesis, structure and biological properties

Two new ferrocenyl-cymantrenyl bimetallic chalcones, [(CO)3Mn(eta5-C5H4)C(O)CHCH(eta5-C5H4)Fe(eta5-C5H5)] (1) and [{(CO)3Mn(eta5-C5H4)C(O)CHCH(eta5-C5H4)}2Fe] (2) have been synthesized. Their reactivity study with triphenylphosphine and bis-(diphenylphosphino)ferrocene led to the isolation of phosphine substituted bimetallic chalcones (3-6). Single crystal X-ray structural characterization for 1 and its phosphine analogue (3) reveals their different conformational identity with anti-conformation for 1, while syn-conformation for 3. Investigation of antimalarial and antibacterial activities was carried out for compounds 1 and 2 against two strains of Plasmodium falciparum (3D7, K1) and four bacterial strains. TD-DFT calculation was performed for compound 1 and electrochemical properties were studied for bimetallic chalcone compounds by cyclic voltammetric technique.

Ferrocenyl-cymantrenyl hetero-bimetallic chalcones: Synthesis, structure and biological properties

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A simple synthesis of metallocene aldehydes from lithiometallocenes and N,N-dimethylformamide: ferrocene and ruthenocene aldehydes and 1,1′-dialdehydes

Lithioferrocene, 1,1′-dilithioferrocene, lithioruthenocene and 1,1′-dilithioruthenocene all react with N,N-dimethylformamide in diethyl ether to produce the respective aldehydes.The lithiation of the two metallocenes can be steered to maximize the formation of only one of the two aldehydes by choosing either n-butyllithium in the presence of tetramethylethylenediamine (TMEDA) or t-butyllithium (tBuLi) as the metallating reagent: ferrocene mono-aldehydes or 1,1′-dialdehydes are formed with good yields (91percent and 85percent respectively, based on ferrocene), lower yields (50percent) of ruthenocene-1,1′-dialdehyde were obtained under the standard conditions, because the 1,3,1′-trialdehyde also formed in significant (19percent) amounts.Monolithiation by nBuLi and the formation of the ruthenocene monoaldehyde (yield, 66percent) are favoured when TMEDA is used in only catalytic amounts; lithiation of ruthenocene by tBuLi selectively leads to monolithioruthenocene and the mono-aldehyde (yield, 91percent).The products are easily purified by column chromatography.The simplicity and the high yield of these reactions make them much more desirable than the previously known multistep procedures.

A simple synthesis of metallocene aldehydes from lithiometallocenes and N,N-dimethylformamide: ferrocene and ruthenocene aldehydes and 1,1′-dialdehydes

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