Coordination chemistry of perhalogenated cyclopentadienes and alkynes. Part 30. New high-yield syntheses of monochloroferrocene and 1,2,3,4,5-pentachloroferrocene. Molecular structures of 1,2-dichloroferrocene and 1,2,3-trichloroferrocene

Bernhartzeder, Stefanie; Sünkel, Karlheinz

doi:10.1016/j.jorganchem.2012.06.016

Cited by 20 publications

(25 citation statements)

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“…Analyte solutions were between 0.1-1 mM. 18 A mixture of ferrocene (4.00 g, 21.5 mmol, 1 eq), potassium tert-butoxide (0.03 g, 2.68 mmol, 0.12 eq.) and THF (120 mL) was stirred in an oven-dried 250 mL three-necked flask and cooled to -78°C (acetone/dry ice).…”

Section: Experimental General Considerationsmentioning

confidence: 99%

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The Unusual Redox Properties of Fluoroferrocenes Revealed through a Comprehensive Study of the Haloferrocenes

Inkpen

Hildebrand

et al. 2015

Organometallics

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ABSTRACT:We report the synthesis and full characterization of the entire haloferrocene (FcX) and 1,1'-dihaloferrocene (fcX 2 ) series (X = I, Br, Cl, F; Fc = ferrocenyl, fc = ferrocene-1,1'-diyl). Finalization of this simple, yet intriguing set of compounds has been delayed by synthetic challenges associated with the incorporation of fluorine substituents. Successful preparation of fluoroferrocene (FcF) and 1,1'-difluoroferrocene (fcF 2 ) were ultimately achieved using reactions between the appropriate lithiated ferrocene species and N-fluorobenzenesulfonimide (NFSI). The crude reaction products, in addition to those resulting from analogous preparations of chloroferrocene (FcCl) and 1,1'-dichloroferrocene (fcCl 2 ), were utilized as model systems to probe the limits of a previously reported 'oxidative purification' methodology. From this investigation and careful solution voltammetry studies, we find that the fluorinated derivatives exhibit the lowest redox potentials of each of the FcX and fcX 2 series. This counter-intuitive result is discussed with reference to the spectroscopic, structural and first principles calculations of these and related materials.

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Section: Experimental General Considerationsmentioning

confidence: 99%

“…FcCl 18 and fcCl 2 5a were accordingly prepared by the reaction of hexachloroethane at -78°C with FcLi or fcLi 2 -TMEDA, respectively (Scheme 1). Subsequent extraction of the crude reaction material with n-hexane provided mixtures of FcH and FcCl, or FcH, FcCl, and fcCl 2 .…”

mentioning

confidence: 99%

The Unusual Redox Properties of Fluoroferrocenes Revealed through a Comprehensive Study of the Haloferrocenes

Inkpen

Hildebrand

et al. 2015

Organometallics

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“…Enantiomers of diols 10a were prepared from the corresponding chiral bisoxazoles 4 and 5 , respectively . Treatment of 4 with sec ‐BuLi in the presence of TMEDA followed by Cl 3 CCCl 3 gave the corresponding 6a‐RR in 49% yield . Similarly, 8a‐SS was obtained in 52% yield from 5 .…”

Section: Resultsmentioning

confidence: 99%

“…After addition, the resulting reaction mixture was stirred at −78 °C for 4 h and then at 0 °C for 30 min to ensure complete dilithiation. Hexachloroethane (0.55g, 2.6 mmol) was added with a syringe to the solution of dilithiated species at 0 °C and the mixture was stirred at rt overnight. The solvent was removed in vacuo and the residue was dissolved in CH 2 Cl 2 (60 mL).…”

Section: Methodsmentioning

confidence: 99%

Double‐stranded ladderphanes with C₂‐symmetric planar chiral ferrocene linkers

Zhang

Liu

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

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Eight ladderphanes with C 2 -symmetric planar chiral ferrocene linkers are synthesized by ring opening metathesis polymerization of bisnorbornene monomers using Grubbs-I catalyst. The aminobenzoate in both monomers and polymers shows absorption maximum around 320 nm. Both monomers and polymers are Circular dichroism (CD) active. Little enhancements of CD profiles around 320 nm are observed for ladderphanes having chiral chloro-or phenyl-substituted ferrocene linkers. However, ladderphanes with a phenyl substituent on the cyclopendienyl ring exhibits enhancement of CD curves aound 240-300 nm. The congested phenyl moieties in adjacent linkers in this polymer might be well oriented such that interactions between these aromatic substituents on different monomeric units might provoke the enhancement of the CD curves in this region. When the methyl-substituted cyclopendienyl ligand is used for chiral ferrocene linkers, the ladderphanes exhibit two-fold enhancement of CD spectrum around 320 nm. This enhancement is further increased when the cyclopentadienyl ligand contains an additional phenyl substituent, owing to exciton coupling between aminobenzoate moieties in adjacent monomeric units. Moreover, the intensity of the CD curves in the region of 240-300 nm is significantly increased. These results suggest that the later polymer may adopt a posible helical structure.

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“…Dies mag bisher zum großen Teil daran gelegen haben, dass diese Verbindungen bis vor kurzem nur in sehr geringen Ausbeuten in Reinform isoliert werden konnten, so dass ihre Verwendung als Ausgangsmaterialien wenig attraktiv erschien. Uns gelang es kürzlich, die Ausbeuten der Reinverbindungen deutlich zu steigern [1]. Im Zusammenhang mit einem anderen von uns untersuchten Arbeitsgebiet, nämlich der Chemie der Pyridylmetallocene [14 -16], interessierte uns die Frage, ob neben dem von uns bereits beschriebenen Pyridyl-monochlorferrocen [CpFe{C 5 H 3 Cl(C 5 H 4 N)}] [14] auch die höher chlorierten Pyridylferrocene zugänglich sind, und welche Eigenschaften sie aufweisen.…”

Section: Introductionunclassified

Komplexchemie perhalogenierter Cyclopentadiene und Alkine, Teil 31 [1]. Darstellung von 2,3-Dichlor- und 2,3,4-Trichlor-1-(2-pyridyl)ferrocen [CpFe{C5H2-nCl2+n(2-C₅H₄N)}] (n=0, 1). Molekülstrukturen von [Cpe{C₅HCl₃(2-C₅H₄N)}] und {C₅HCl₂(PPh₃)(2-C₅H₄N)g, einem unerwarteten Nebenprodukt / Coordination Chemistry of Perhalogenated Cyclopentadienes and Alkynes, Part 31. Synthesis of 2,3-Dich

Sünkel

Weigand

2012

Zeitschrift Für Naturforschung B

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Lithiation of 1,2-dichloro-or 1,2,3-trichloroferrocene with lithium tetramethylpiperidinide, followed by transmetallation with ZnCl 2 and Pd(II)-catalyzed coupling with 2-bromopyridine, yield the pyridylferrocenes [CpFe{C 5 H 2−n Cl 2+n (2-C 5 H 4 N)}] (2a, b, n = 0 or 1) as brown oils of low stability. Recrystallization of 2b produced a small number of X-ray quality crystals, which could be shown to have the proposed constitution. However, from the recrystallization solution of 2a a few crystals precipitated whose X-ray structure determination identified them as a metal-free phosphonium ylide {C 5 HCl 2 (2-C 5 H 4 N)(PPh 3 )} (3).

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Coordination chemistry of perhalogenated cyclopentadienes and alkynes. Part 30. New high-yield syntheses of monochloroferrocene and 1,2,3,4,5-pentachloroferrocene. Molecular structures of 1,2-dichloroferrocene and 1,2,3-trichloroferrocene

Cited by 20 publications

References 18 publications

The Unusual Redox Properties of Fluoroferrocenes Revealed through a Comprehensive Study of the Haloferrocenes

The Unusual Redox Properties of Fluoroferrocenes Revealed through a Comprehensive Study of the Haloferrocenes

Double‐stranded ladderphanes with C₂‐symmetric planar chiral ferrocene linkers

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Coordination chemistry of perhalogenated cyclopentadienes and alkynes. Part 30. New high-yield syntheses of monochloroferrocene and 1,2,3,4,5-pentachloroferrocene. Molecular structures of 1,2-dichloroferrocene and 1,2,3-trichloroferrocene

Cited by 20 publications

References 18 publications

The Unusual Redox Properties of Fluoroferrocenes Revealed through a Comprehensive Study of the Haloferrocenes

The Unusual Redox Properties of Fluoroferrocenes Revealed through a Comprehensive Study of the Haloferrocenes

Double‐stranded ladderphanes with C2‐symmetric planar chiral ferrocene linkers

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Double‐stranded ladderphanes with C₂‐symmetric planar chiral ferrocene linkers