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Efficient regio- and diastereo-controlled synthesis of 1,1?- and 1,1?,2,2?-functionalised ferrocenes and the formation of 2-oxa[3]ferrocenophanes

The synthesis of a C2 symmetric 1,1? ,2,2?-tetrasubstituted ferrocene system was discussed. The route involved the reduction of ferrocenyl carbonyl compounds which gave access to a range of alcohols, alkenes, alkanes, ethers, and 2-oxa[3]ferrocenophanes depending on the precise conditions used. The loss of optical activity of 1,1?-bis(hydroxymethyl)ferrocenes and 1,1?-bis(hydroxymethyl)ruthenocenes, which had been prepared by asymmetric reduction, was demonstrated in an acidic medium by extensive 1H NMR studies.

Efficient regio- and diastereo-controlled synthesis of 1,1?- and 1,1?,2,2?-functionalised ferrocenes and the formation of 2-oxa[3]ferrocenophanes

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Reference£º
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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Synthesis and physico-analytical studies of some novel ferrocenyl Schiff base derivatives

A series of ferrocenyl Schiff base derivatives was synthesized by condensation reactions of 1,1?-ferrocenedicarboxaldehyde and aromatic amines containing long chain alkyl groups as free ends which were characterized by their physical properties, elemental, FTIR, 1H NMR, 13C NMR spectral and thermal analysis. The thermal behaviour of the synthesized compounds was studied by differential scanning calorimetry (DSC) which revealed that these compounds may exhibit mesomorphic properties. The DSC results of aromatic amines and ferrocenyl Schiff bases were compared to study the effects of structure, i.e. rigid core and terminal chain length, on the phase transition behaviour.

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Reference£º
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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Metal-directed assembly of polyferrocenyl transition metal dithiocarbamate macrocyclic molecular boxes

Novel redox-active polyferrocenyl transition metal dithiocarbamate macrocyclic molecular boxes (10a-c), (11) and (12a-c) are synthesised by reaction of the respective ferrocenyl secondary amines, namely, N,N?-bis(ferrocenemethyl)-1,3-bis(aminomethyl)benzene (4), 1,1?-bis(benzylaminomethyl)ferrocene (8) and 1,1?-bis((ferrocenylmethyl)aminomethyl)ferrocene (9) with carbon disulfide, potassium hydroxide and transition metal (zinc, copper, nickel) acetate in high yields (52-82%) and characterised by spectroscopic and electrochemical techniques. The single-crystal X-ray structure of 10a shows that each zinc atom is in tetrahedral geometry, being bonded to two dithiocarbamate ligands with Zn-S distances 2.32(1)-2.44(1) A.

Metal-directed assembly of polyferrocenyl transition metal dithiocarbamate macrocyclic molecular boxes

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Reference£º
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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Preparation, characterization and electrochemical and X-ray structural studies of new conjugated 1,1?-ferrocenediyl-ended [CpFe-arylhydrazone] + salts

A series of new conjugated bimetallic ferrocenyl 1,1?-bis- substituted compounds of the type (E)-[CpFe(eta6-p-RC 6H4)NHN=CH(eta5-C5H 4)Fe(eta5-C5H4)-CH=CHC 6H4-p-R?]+PF6- (Cp = eta5-C5H5; R, R? = H, NO 2, 11; Me, NO2, 12; MeO, NO2, 13; Cl, NO 2, 14; Me, CN, 15; Me, Me, 16), with end-capped (E)-ethenylaryl and [CpFe(arylhydrazone)]+ substituents, have been prepared by the condensation reaction of 1,1?-(p-R?-arylethenyl) ferrocenecarboxaldehyde (R? = Me, 4; NO2, 5; CN, 6) with the organometallic hydrazine precursors [CpFe(eta6-p-RC 6H4NHNH2)]+PF6 – (R = H, 7; Me, 8; MeO, 9; Cl, 10). In the trimetallic series, {[CpFe(eta6-p-RC6H4)NHN=CH(eta 5-C5H4)]2Fe}2+[PF 6-]2 (R = H, 17; Me, 18; MeO, 19, Cl, 20), which results from the condensation of two equivalents of the same organometallic hydrazine precursor (7-10) with 1,1?- ferrocenedicarboxaldehyde, the ferrocenediyl core symmetrically links two cationic mixed-sandwich units. These ten hydrazones (11-20) were stereoselectively obtained as their trans isomers about the N=C double bond. All the new compounds were thoroughly characterized by a combination of elemental analysis, spectroscopic techniques (1H NMR, IR and UV-Vis) and electrochemical studies in order to prove electronic interaction between the donating and accepting units through the pi-conjugated system. A representative example of each series has also been characterized by single crystal X-ray diffraction analysis. The bimetallic complex 16+ adopts an anti conformation with the two iron atoms on opposite faces of the dinucleating hydrazonato ligand, whereas the trinuclear complex 192+ adopts a syn conformation with an Fe-Fe-Fe angle of 180. Other salient features of these structures are the long Fe-Cipso bond distances and the slight cyclohexadienyl character at the coordinated C6 ring, with a folding angle of 7.4 and 7.0 for 16+ and 19 2+, respectively.

Preparation, characterization and electrochemical and X-ray structural studies of new conjugated 1,1?-ferrocenediyl-ended [CpFe-arylhydrazone] + salts

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Reference£º
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-stranded 1D-coordination polymer assembled using the tetravergent ligand 1,1?-bis(4,2?:6?,4?-terpyridin-4?-yl)ferrocene

1,1?-Bis(4,2?:6?,4?-terpyridin-4?-yl)ferrocene (1) reacts with ZnCl2 to yield a double-stranded 1D-coordination polymer [{Zn2(1)Cl4}?3CHCl3]n. The 1,1?-functionalized ferrocene core adopts a cisoid-conformation, giving rise to a folded conformation for 1 and a double-stranded 1D-polymer chain. This contrasts with previously reported multi-stranded chains supported by 4,2?:6?,4?-terpyridine ligands in which the multiple-nature of the chain arises from multinuclear metal nodes.

A double-stranded 1D-coordination polymer assembled using the tetravergent ligand 1,1?-bis(4,2?:6?,4?-terpyridin-4?-yl)ferrocene

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Reference£º
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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Synthesis and characterization of new ferrocenyl bishydrazones

New ferrocenyl bishydrazones (2a-2d) have been efficiently obtained from 1,1′-ferrocenedicarboxaldehyde by a straightforward synthesis. The four new compounds have been fully characterized by NMR (1H, 13C), high-resolution mass spectroscopy, and the molecular structure of compounds (2a-2d) has been elucidated by X-ray diffraction on single crystals.

Synthesis and characterization of new ferrocenyl bishydrazones

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Reference£º
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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Triggered Metal Ion Release and Oxidation: Ferrocene as a Mechanophore in Polymers

The introduction of mechanophores into polymers makes it possible to transduce mechanical forces into chemical reactions that can be used to impart functions such as self-healing, catalytic activity, and mechanochromic response. Here, an example of mechanically induced metal ion release from a polymer is reported. Ferrocene (Fc) was incorporated as an iron ion releasing mechanophore into poly(methyl acrylate)s (PMAs) and polyurethanes (PUs). Sonication triggered the preferential cleavage of the polymers at the Fc units over other bonds, as shown by a kinetic study of the molar mass distribution of the cleaved Fc-containing and Fc-free reference polymers. The released and oxidized iron ions can be detected with KSCN to generate the red-colored [Fe(SCN)n(H2O)6?n)](3?n)+ complex or reacted with K4[Fe(CN)6] to afford Prussian blue.

Triggered Metal Ion Release and Oxidation: Ferrocene as a Mechanophore in Polymers

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Reference£º
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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Paramagnetic and semiconducting 1:1 salts of 1,1?-disubstituted ferrocenes and [Ni(mnt)2]-. Synthesis, structure, and physical properties

The ferrocene-based electron donors 1,1?-bis[2-(4-(methylthio)phenyl)-CE)-ethenyl]ferrocene (2), 1,1?-bis[2-(4-methoxyphenyl)-CE)-ethenyl]ferrocene (3), 1,1?-bis[(1,3-dithiolo[4,5-b][1,3]-dithiol-2-ylidene)methyl]ferrocene (4), and 1,1?-bis[(1,3-benzodithiol-2-ylidene)methyl]ferrocene (5) were found to react with ferrocenium bis(maleonitriledithiolato)nickelate (1-) ([FeCp2]+[Ni(mnt)2]-, 6) to afford the corresponding 1:1 paramagnetic salts 7-10, containing 1,1?-disubstituted ferrocenium derivatives. SQUID magnetic susceptibility measurements of these new compounds showed a behavior dominated by antiferromagnetic interactions within pairs of [Ni(mnt)2]- ions. Pressed pellets of compounds 7 ([2][Ni(mnt)2]) and 9 ([4]-[Ni(mnt)2]) are semiconducting, with a relatively large conductivity activation energy (0.85 and 1.13 eV). Crystals of 7 reveal the monodimensional nature of the compound. Each separate stack of [Ni(mnt)2]- ions is flanked by two ferrocenium stacks. Ni-Ni distances alternate between 3.67 and 3.99 A.

Paramagnetic and semiconducting 1:1 salts of 1,1?-disubstituted ferrocenes and [Ni(mnt)2]-. Synthesis, structure, and physical properties

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Reference£º
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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Reference 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 an article, 1271-48-3, molcular formula is C12H10FeO2, belongs to iron-catalyst compound, introducing its new discovery.

heterodi- and heterotrimetallic compounds containing five-membered rings and sigma(Pd-Csp2, ferrocene) bonds. X-ray crystal structure of the meso-form of [Pd2{Fe[(eta5-C5H3)-C(CH 3)=N-C6H5]}2Cl2(PPh 3)2]

The syntheses and characterization of heterodi- and heterotrimetallic complexes of general formulas [Pd{[(eta5-C5H 3)-C(R)=N-R?]Fe[(eta5-C5H 4)-C(R)=N-R?]}Cl(PPh3)] [Pd{[(eta5-C5H3)C(C6H 5)=N-C6H5]Fe[(eta5-C 5H4)-C(O)=N-C6H5]}Cl(PPh 3)], and [Pd2{Fe[(eta5-C5H3)-C(R)= N-R?]2}Cl2(PPh3)2] {with R = H, CH3, or C6H5 and R?= phenyl or benzyl groups} are reported. The X-ray crystal structure of the meso-form of [Pd2{Fe[(eta5-C5H3)-C(CH 3)=N-C6H5]2}Cl2(PPh 3)2] (2b) is also described.

heterodi- and heterotrimetallic compounds containing five-membered rings and sigma(Pd-Csp2, ferrocene) bonds. X-ray crystal structure of the meso-form of [Pd2{Fe[(eta5-C5H3)-C(CH 3)=N-C6H5]}2Cl2(PPh 3)2]

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Reference£º
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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An Efficient Synthesis of the First Electroactive Phosphorus-containing Bisferrocene Macrocycles

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.

An Efficient Synthesis of the First Electroactive Phosphorus-containing Bisferrocene Macrocycles

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Reference£º
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