Can You Really Do Chemisty Experiments About 1,1′-Ferrocenedicarboxaldehyde

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Highly enantioselective one-pot synthesis of chiral tri- and tetrasubstituted ferrocenes from 1,1′-ferrocenedicarbaldehyde

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)].

Highly enantioselective one-pot synthesis of chiral tri- and tetrasubstituted ferrocenes from 1,1′-ferrocenedicarbaldehyde

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Synthesis and Structural Characterization of a Bitopic Ferrocenyl-Linked Bis(pyrazolyl)methane Ligand and Its Silver(I) Coordination Polymers

The bitopic ligand 1,1?-bis(dipyrazol-1-ylmethyl)ferrocene, Fe[C 5H4CH(pz)2]2 (1; pz = pyrazolyl ring), has been prepared by the reaction of 1,1?-ferrocenedicarbaldehyde and 1,1?-carbonyldipyrazole. In the solid state, the bis(pyrazolyl) methane moieties are in an antiperiplanar eclipsed orientation. The molecules are organized into a three-dimensional array by pi…pi, weak C-H-…N hydrogen bonding, and C-H…pi interactions. The reactions between 1 and AgBF4, AgPF6, AgSO3CF 3, or AgSbF6 yield {Fe[C5H 4CH(pz)2]2AgBF4}n (2), {Fe[C5H4CH(pz)2]2AgPF 6}n (3), {Fe[C5H4CH(Pz) 2]2AgSO3CF3}n (4), and {Fe[C5H4CH(pz2]2AgSbF 6}n (5), respectively. The solid-state structures consist of coordination polymers with compounds 2 and 3 arranged in helical chains, while the chains in 3¡¤1/2Et2O, 4¡¤1.5C6H 6,5¡¤1/2Et2Et2O, and 5¡¤1/2C 6H6 are nonhelical. In these structures, the ferrocenyl groups adopt a similar orientation, where the angle between CH(pz)2 groups is confined to the range of 85-99 and the silver pyrazolyl coordination spheres are also in very similar distorted-tetrahedral arrangements. Both structural types form three-dimensional supramolecular structures organized by weak hydrogen bonds, pi…pi stacking, and CH…pi interactions. In the helical form, the anions reside in the pockets formed by the close-packed chains, whereas in the nonhelical form, sizable channels, which contain the solvent molecules and the anions, are located between the chains.

Synthesis and Structural Characterization of a Bitopic Ferrocenyl-Linked Bis(pyrazolyl)methane Ligand and Its Silver(I) Coordination Polymers

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Coordination assembled rings of ferrocene-bridged trisporphyrin with flexible hinge-like motion: Selective dimer ring formation, its transformation to larger rings, and vice versa

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.

Coordination assembled rings of ferrocene-bridged trisporphyrin with flexible hinge-like motion: Selective dimer ring formation, its transformation to larger rings, and vice versa

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Syntheses, structures of N-(substituted)-2-aza-[3]-ferrocenophanes and their application as redox sensor for Cu2+ ion

Rigid N-(substituted)-2-aza-[3]-ferrocenophanes L1 and L2 were easily synthesized from 1,1 -dicarboxyaldehydeferrocene and the corresponding amines. Ligands L1 and L2 were characterized by 1H NMR, 13C NMR and single-crystal X-ray crystallography. The coordination abilities of L1 and L2 with metal ions such as Cu2+, Mg2+, Ni2+, Zn2+, Pb2+ and Cd2+ were evaluated by cyclic voltammetry. The electrochemical shift (DeltaE1/2) of 125 mV was observed in the presence of Cu2+ ion, while no significant shift of the Fc/Fc + couple was observed when Mg2+, Ni2+, Zn 2+, Pb2+, Cd2+ metal ions were added to the solution of L1 in the mixture of MeOH and H2O. Moreover, the extent of the anodic shift of redox potentials was approximately equal to that induced by Cu2+ alone when a mixture of Cu2+, Mg2+, Ni2+, Zn2+, Pb2+ and Cd2+ was added to a solution of L1. Ligand L1 was proved to selectively sense Cu2+ in the presence of large, excessive first-row transition and late-transition metal cations. The coordination model was proposed from the results of controlled experiments and quantum calculations.

Syntheses, structures of N-(substituted)-2-aza-[3]-ferrocenophanes and their application as redox sensor for Cu2+ ion

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Reductive deoxygenation of alpha-ferrocenyl carbonyls and alcohols to alkylferrocenes by borane-dimethyl sulfide

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.

Reductive deoxygenation of alpha-ferrocenyl carbonyls and alcohols to alkylferrocenes by borane-dimethyl sulfide

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Synthesis, structural characterization and electrochemical study of 1,1?-ferrocenylene labeled amino acids

Unsymmetrical 1,1?-disubstituted ferrocenes bearing an amino acid moiety and a conjugated electron density controlling substituent were synthesized conveniently starting from 1,1?-ferrocenedicarbaldehyde. The novel ferrocene amino acid derivatives were completely characterized from their MS, 1H NMR and 13C NMR spectra. Their electrochemical behavior was studied by cyclic voltammetry. Their formal redox potentials Ef were slightly influenced by the nature of the amino acid and mainly by the kind of the ethenyl substituent. Furthermore all the (Z)-isomers exhibited a slight anodic shift compared with the corresponding (E)-isomers.

Synthesis, structural characterization and electrochemical study of 1,1?-ferrocenylene labeled amino acids

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An electroactive nitrogen-rich [4.4]ferrocenophane displaying redox-switchable behavior: Selective sensing, complexation, and decomplexation of Mg2+ ions

A chameleonic, redox-switchable carrier molecule: A [4,4]ferrocenophane ligand can selectively recognize Mg2+ ions through complexation. This ligand can transport and release Mg2+ ions by application of an external electrochemical stimulus across a CH2Cl2 liquid membrane (see picture). Furthermore, dramatic color changes are seen, which allow the potential for “naked-eye” detection. (Chemical Equation Presented).

An electroactive nitrogen-rich [4.4]ferrocenophane displaying redox-switchable behavior: Selective sensing, complexation, and decomplexation of Mg2+ ions

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Pd-mediated synthesis of linked conjugated tri- and penta-ferrocenyl complexes

A facile synthesis of new conjugated oligo-ferrocenyl compounds is described. The synthetic method consists of a two step procedure, which combines olefination by the Wittig procedure and Pd-mediated C-C coupling, leading to high yields of tri- and penta-ferrocenyl complexes. The crystal structures of the 1,1?-bissubstituted ferrocenyl precursors are described. The electrochemical analysis of the compounds obtained, reveals that the peripheral ferrocenyl units display an equivalent redox behavior, with a large separation of the peak corresponding to the central ferrocenyl unit.

Pd-mediated synthesis of linked conjugated tri- and penta-ferrocenyl complexes

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Mechanochemical synthesis and spectroscopic properties of 1,1′-ferrocenyldiacrylonitriles: The effect of para -substituents

An efficient and simple solvent-free mechanochemical approach for the synthesis of 1,1′-ferrocenyldiacrylonitriles was achieved by grinding together 1,1′-ferrocenedicarboxaldehyde (1) and phenylacetonitriles. A range of 1,1′-ferrocenyldiacrylonitriles and ferrocenylacrylonitriles (2-7) were synthesized within short reaction times, with water as the only by-product. In a similar manner, grinding together ferrocenemonocarboxaldehyde (8) and phenylenediacetonitrile yielded phenylene-3,3′-bis-(ferrocenyl)diacrylonitrile (9) and 3-ferrocenyl-2-(acetonitrophenyl)acrylonitrile (10). The yield and selectivity towards formation of ferrocenyldiacrylonitriles was strongly influenced by the electronegativity of the para-substituent on the phenyl ring of phenylacetonitriles. The compounds were characterized using NMR, IR, and UV-visible spectroscopy and HR-MS. Cyclic voltammetry measurements of selected compounds highlighted the role of ligands in tuning the electrochemical properties of 1,1′-ferrocenyldiacrylonitriles. X-ray crystallographic analysis highlighted the effect of the electronegativity of the para-substituent on the conformation of cyclopentadienyl rings attached to a ferrocenyl moiety.

Mechanochemical synthesis and spectroscopic properties of 1,1′-ferrocenyldiacrylonitriles: The effect of para -substituents

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The remarkable behavior of crystalline [Fe(eta5-C5H4CHO)2]: Two solid-to-solid phase transitions and a solid-state reaction

The crystal architecture, stability, and behavior with temperature of bis(formyl)ferrocene, [Fe(eta5-C5H4CHO)2], have been investigated by variable-temperature X-ray diffraction experiments, differential scanning calorimetry, and thermogravimetry experiments. [Fe(eta5-C5H4CHO)2] is present with two independent molecules with cisoid and transoid relative orientations of the two formyl groups in the crystals obtained from the reaction sequence (phase RT-1). The role of C-H- – -O interactions involving the formyl groups has been examined. When RT-1 is heated, the first irreversible phase transition to a plastic phase (phase HT) is observed at ca. 38C (311 K). When it is cooled, phase HT transforms into a new room-temperature phase (RT-2). Once RT-2 has been formed, the system switches reversibly between HT and RT-2 (transition temperature in the heating cycles ca. 35C), while RT-1 can no longer be obtained. Further heating of phase HT shows the occurrence of an exothermic reaction at ca. 150C (423 K) leading to the formation of a ferrocene-based polymer.

The remarkable behavior of crystalline [Fe(eta5-C5H4CHO)2]: Two solid-to-solid phase transitions and a solid-state reaction

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