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Stereospecific synthesis, structural characterisation and resolution of 2-phospha[3]ferrocenophane derivatives – A new chiral scaffold

The first 2-phospha[3]ferrocenophanes containing stereogenic carbon atoms in the three-atom bridge have been synthesised from phenylphosphane by stereospecific ring-closing phosphanation reactions. Either alpha-substituted 1,1?-bis-(hydroxymethyl)ferrocenes or the corresponding 2-oxa-[3]ferrocenophanes have been used as diastereomerically pure starting materials. The resolution of 1,2,3-triphenyl-[2]phosphaferrocenophane has been achieved by chromatographic separation of the diastereomeric adducts of a chiral cyclopalladate complex. The X-ray crystal structures of two 2-phospha[3]ferrocenophane-borane complexes are also reported. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.

Stereospecific synthesis, structural characterisation and resolution of 2-phospha[3]ferrocenophane derivatives – A new chiral scaffold

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In heterogeneous catalysis, catalysts provide a surface to which reactants bind in a process of adsorption. In homogeneous catalysis, catalysts are in the same phase as the reactants. Recommanded Product: 12180-80-2. Catalysts allow a reaction to proceed via a pathway that has a lower activation energy than the uncatalyzed reaction. Introducing a new discovery about 12180-80-2, Name is 1,1′-Dibenzoylferrocene

Accurate redeterminations of 1,1?-dibenzoylferrocene and (4-nitrophenyl)-ferrocene

In the solid state, molecules of 1,1?-dibenzoylferrocene, [Fe(Cl12H9O)2], (I), are linked to form infinite chains in the [100] direction via (cyclopentadienyl)C – H…O hydrogen bonds [C…O 3.354 (4) A]. In the structure of (4-nitrophenyl)ferrocene, [Fe(C5H5)(C11H8NO2)], (II), there are no C – H-…O hydrogen bonds and molecules are separated by normal van der Waals distances. For earlier determinations see Struchkov [Dokl. Akad. Nauk SSSR (1956), 110, 67-70] for (I) and Roberts et al. [J. Chem. Soc. Dalton Trans. (1988), pp. 1549-1556] for (II).

Accurate redeterminations of 1,1?-dibenzoylferrocene and (4-nitrophenyl)-ferrocene

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In heterogeneous catalysis, catalysts provide a surface to which reactants bind in a process of adsorption. In homogeneous catalysis, catalysts are in the same phase as the reactants. Application In Synthesis of 1,1′-Dibenzoylferrocene. Catalysts allow a reaction to proceed via a pathway that has a lower activation energy than the uncatalyzed reaction. Introducing a new discovery about 12180-80-2, Name is 1,1′-Dibenzoylferrocene

Simple reduction of ferrocenyl aldehydes and ketones by sodium boranuide in trifluoroacetic acid: New, efficient, general preparation of alkylferrocenes

Alkylferrocenes are obtained in excellent yields by ionic hydrogenation of ferrocenyl aldehydes and ketones using sodium boranuide and trifluoroacetic acid.

Simple reduction of ferrocenyl aldehydes and ketones by sodium boranuide in trifluoroacetic acid: New, efficient, general preparation of alkylferrocenes

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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)…

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.

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)…

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Metal complexes of biologically important ligands. CLXVI [1] metal complexes with ferrocenylmethylcysteinate and 1,1?-ferrocenylbis- (methylcysteinate) as ligands

A series of complexes of transition metal ions (Cr3+, Mn 2+, Co2+, Ni2+, Cu2+, Zn 2+) and of lanthanide ions (La3+, Nd3+, Gd 3+, Dy3+, Lu3+) with the anions of ferrocenylmethyl-L-cysteine [(C5H5)Fe(C5H 4CH(R)SCH2CH(NH3+)CO 2-] (L1) and with the dianions of 1,1?-ferrocenylbis(methyl-L-cysteine) [Fe(C5H 4CH(R)SCH2CH(NH3+) CO 2-)2] (R = H, Me, Ph) (L2) as N,O,S-donors were prepared. With the monocysteine ferrocene derivative L 1 as ligands complexes [MIIL12] or [CrIIIL12]Cl type complexes are formed whereas the bis(cysteine) ligand L2 yields insoluble complexes of type [ML2]n, presumably as coordination polymers. The magnetic moments of [MnIIL2]n, [PrIIIL 2]n(OH)n and [DyIIIL 2]n(OH)n exhibit “normal” paramagnetism.

Metal complexes of biologically important ligands. CLXVI [1] metal complexes with ferrocenylmethylcysteinate and 1,1?-ferrocenylbis- (methylcysteinate) as ligands

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Acyl-substituted ferrocenes as driers for solvent-borne alkyd paints

Ferrocenes bearing acyl substituents in the cyclopentadienyl rings [Fe(eta5-C5H4COR)(eta5-C 5H5)] and [Fe(eta5-C5H 4COR)2] (R = CH3, CF3 and Ph) were examined as new driers for solvent-borne alkyd binder. All studied ferrocenes were found to be active catalysts for cross-linking reaction of the alkyd. These iron(II) compounds give solid polymeric films with hardness and drying time comparable to the commercial cobalt(II) drier. Acetyl- and benzoyl-substituted ferrocenes show an excellent synergic effect with the cobalt drier giving hard polymeric films within short drying time. The kinetics of the alkyd autoxidation was followed by FTIR spectroscopy. Spin-trapping ESR technique has proven the important role of the ferrocenium cation upon decomposition of hydroperoxides by ferrocene-based driers. The peroxy and alkoxy radicals, appearing in drying process, were resolved by the new spin trap methyl-N-mesityl nitrone.

Acyl-substituted ferrocenes as driers for solvent-borne alkyd paints

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Enantioselective reduction of benzoyl derivatives of ferrocene and ruthenocene: optically active carbinols and carbenium ions

Mono- and 1,1′-disubstituted metallocenes, XC5H4MC5H4Y, M = Fe, Ru, X = H, Y = COPh, or X = Y = COPh, have been reduced using the LiAlH4-Chirald complex to afford the corresponding carbinols and diols enantiomerically enriched.Optical yield was 53percent for benzoylferrocene and 86percent for benzoylruthenocene, (R)-configuration being predominant.Monocations had an opposite sign of rotation and were stable in CF3COOH.On the contrary, diols have lost optical rotation in the same acid that has been explained by formation of the achiral ether intermediate.Dication has been formed in DSO3F as evidenced by the 1H NMR spectrum but it is completely racemized even at low temperature.

Enantioselective reduction of benzoyl derivatives of ferrocene and ruthenocene: optically active carbinols and carbenium ions

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Ferrocene-containing acetylenic peroxy alcohols

Lithium tert-alkylperoxyacetylides were reacted with acetyl-, benzoyl, and 1,1?-dibenzoylferrocenes to obtain previously unknown ferrocene-containing acetylenic mono- and diperoxy alcohols. Thermal stability of the products was evaluated.

Ferrocene-containing acetylenic peroxy alcohols

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Substituent effects on ferrocenes in aluminum chloride-butylpyridinium chloride molten-salt mixtures

The visible absorption spectra and reduction potentials of 11 ferrocenes containing electron-withdrawing substituents were determined in an N-n-butylpyridinium chloride-aluminum chloride molten salt. When the substituent(s) on the cyclopentadienyl ring(s) of ferrocene were varied, the reduction potential was caused to range over 1.25 V, and the wavelength for maximum absorption of visible light was varied by nearly 200 nm. These changes are greater than have been observed for similar ferrocenes in other nonaqueous solvents. Evidence is presented for specific interactions of particular ferrocenes with the molten salt.

Substituent effects on ferrocenes in aluminum chloride-butylpyridinium chloride molten-salt mixtures

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A facile synthetic route to (eta5-benzoylcyclopentadienyl)metal compounds

A reaction between cyclopentadienylsodium and ethyl benzoate in refluxing THF produces (benzoylcyclopentadienyl)sodium (4) in 70-80percent yield.Subsequent treatment of 4 in ethanol solution with thallium ethoxide affords (benzoylcyclopentadienyl)thallium (3) in nearly quantitative yield.Reactions of 3 with Mn(CO)5Br, Re(CO)5Br, 2 or FeCl2 lead to the respective eta5-benzoylcyclopentadienyl derivatives of these metals, and demonstrate the utility of 3 in organometallic syntheses.Reactions of several of these organometallic ketones with cymantrenyllithium<(eta5-C5H4Li)Mn(CO)3> provide a useful new route to bimetallic compounds.

A facile synthetic route to (eta5-benzoylcyclopentadienyl)metal compounds

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