Synthesis and Characterization of 1,2,3,4,5-Pentafluoroferrocene

Sünkel, Karlheinz; Weigand, Stefan; Hoffmann, Alexander; Blomeyer, Sebastian; Reuter, Christian G.; Vishnevskiy, Yury V.; Mitzel, Norbert W.

doi:10.1021/ja511588p

Cited by 42 publications

(59 citation statements)

References 49 publications

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“…This observation has, however, been reported in a single publication 6 and needs further verification.…”

Section: (E) First Principles Calculationsmentioning

confidence: 65%

“…All materials were studied by solution voltammetry in MeCN/0.1 M NBu 4 PF 6 , and exhibited essentially reversible behavior (i pa /i pc ~ 1, i p ∝ V s 1/2 ; data summarized in Table 2). A comparison of equilibrium potentials for FcX and fcX 2 show that FcH is easier to oxidize than FcX, which in turn is easier to oxidize than fcX 2 (for the same halide).…”

Section: (B) Electrochemistrymentioning

confidence: 99%

“…6 [FcB(C 6 Cl 5 ) 2 ] has also been observed to exhibit a higher equilibrium potential than [FcB(C 6 F 5 ) 2 ] (E 1/2 = 0.55 V vs. 0.45 V, respectively; though the C 6 Cl 5 group is in this case considered more electron withdrawing). …”

Section: (B) Electrochemistrymentioning

confidence: 99%

“…First we wondered if very electron-withdrawing substituents on the cyclopentadienyl anion (Cp -) ring might hamper its electron-donating ability, so weakening the Cp-Fe bond and reducing the inductive electron-withdrawing effect felt at Fe. A weaker bond would however result in a longer Cp-Fe distance, whereas the X-ray crystal structure of [FeCp(C 5 F 5 )] 6 clearly shows the (C 5 F 5 )-Fe bond is shorter (invalidating this theory). Likewise, any possibility of F-Fe orbital interactions -for example, agostic bonding/p orbital overlap (increasing the electron density at Fe) -appears unlikely following the observation that the fluoride substituents are bent outwards and away from the ferrocene centre.…”

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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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“…This observation has, however, been reported in a single publication 6 and needs further verification.…”

Section: (E) First Principles Calculationsmentioning

confidence: 65%

Section: (B) Electrochemistrymentioning

confidence: 99%

Section: (B) Electrochemistrymentioning

confidence: 99%

mentioning

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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“…Although the effect of fluoride substitution on ferrocene was investigated experimentally [27][28][29], to the best of our knowledge the structural and the optoelectronic properties of ferrocene and fluorine substituted derivatives including FeC 10 H 8 F 2 , FeC 10 H 6 F 4 , FeC 10 H 4 F 6 , FeC 10 H 2 F 8 , and FeC 10 F 10 have not been investigated theoretically. The monoclinic crystal lattice with P21/a (No.…”

Section: Introductionmentioning

confidence: 99%

Ab initio studies of optoelectronic properties of fluorine-substituted ferrocene

2015

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Structural and optoelectronic properties of ferrocene and some derivatives (Fe C 10 X 10 , X = H, F) have been investigated by density functional theory. The full potential linearized augmented plane wave including generalized gradient approximation was used in this study. Since the ferrocene family has appealing photochemical and electrochemical properties, they have been extensively used in electronic and photonic industries. The current study accomplishes the electron density, density of states, and optical calculations. We have found that the optoelectronic properties of ferrocene change under substitution of hydrogen with fluorine. Band gaps of 2.72 and 0.92 eV were obtained for FeC 10 H 10 and FeC 10 F 10 , respectively. The band gap was obviously reduced for the full fluorine-substituted ferrocene compared with the unsubstituted one, which exhibited an increase in the charge transfer properties. Results of the optical calculations also confirm these findings.

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2018

Vibrational Spectra of Organometallics

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Synthesis and Characterization of 1,2,3,4,5-Pentafluoroferrocene

Cited by 42 publications

References 49 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

Ab initio studies of optoelectronic properties of fluorine-substituted ferrocene

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