Structure of ferrocenium hexafluorophosphate

Martínez, Ricardo; Tiripicchio, A.

doi:10.1107/s0108270189005883

Cited by 40 publications

(37 citation statements)

References 10 publications

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“…Remarkably, the bond lengths between Fe2 and the cyclopentadienyl carbon atoms are significantly longer than those in ferrocenium hexafluorophosphate, which shows an average value of 205.1 pm, the mean standard deviations of the analysis being significantly higher than in the case of 2. 20 Although there is no obvious explanation for this large difference, we note that the cyclopentadienyl ligands in ferrocenium hexafluorophosphate adopt an almost perfect staggered conformation (twist angle 33.2 • ), while the corresponding value for the ferrocenium substituent in 2 is -22.9 • , indicating a deviation from the staggered conformation of ca. 10 • .…”

Section: Resultsmentioning

confidence: 92%

One electron oxidation of triferrocenylmethanol: synthesis, metal atom dynamics, electron delocalization, and the crystal structure of [Fc3COH]+ PF6−

Butenschön

Daniliuc

et al. 2011

Dalton Trans.

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The title compound 2 was prepared and its crystal structure was determined at 100 K. The neat solid was examined by temperature dependent 57 Fe Mössbauer effect (ME) spectroscopy over the interval 92 < T < 318 K, and evidences two diamagnetic Fe(II) sites and one paramagnetic Fe(III) site. The latter shows spin-lattice relaxation, but there is no evidence of electron delocalization among the three iron sites in the above temperature interval. The mean-square-amplitude-of-vibration of the diamagnetic iron site has been determined from the recoil-free fraction ME resonance, and compared to the neutral Fc 3 COH homologue (1). The ME dynamical data are in good agreement with the U i,j value at 100 K extracted from the crystallographic results. The ME parameters at 5 K have also been determined with the sample compound embedded in a paraffin wax matrix as well as pelletized with BN.

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Section: Resultsmentioning

confidence: 92%

One electron oxidation of triferrocenylmethanol: synthesis, metal atom dynamics, electron delocalization, and the crystal structure of [Fc3COH]+ PF6−

Butenschön

Daniliuc

et al. 2011

Dalton Trans.

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“…For ferrocene, this term is exceedingly small as the structural changes accompanying the ET process in uncomplexed ferrocene are minimal. [33] The second term is concerned with solvent reorganization, and important differences between free and hemicarcerand-encapsulated ferrocene may Figure 7. Comparison of approximate sizes of ferrocene and a be expected here.…”

Section: Discussionmentioning

confidence: 99%

Electrochemistry of Encapsulated Guests: Ferrocene inside Cram's Hemicarcerands

1998

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The voltammetric behavior of ferrocene encapsulated inside two hemicarcerand hosts was investigated in dichloromethane and tetrachloroethane solutions. Molecular encapsulation led to substantial changes in the anodic voltammetric behavior of the ferrocene nucleus. Generally, encapsulated ferrocene exhibited a more positive halfwave oxidation potential and a lower apparent standard rate constant of heterogeneous electron transfer than uncomplexed ferrocene under identical experimental conditions. Whereas the anodic shift of the half-wave potential probably results from the hindered solvation of the positively charged, oxidized ferrocene inside the nonpolar hemicarcerand cavities, the observed decrease in electron transfer rate seems to arise primarily from the increased molecular mass of the electro-inactive species and the longer distance of maximum approach between the ferrocene center and the electrode surface which is imposed by the encapsulating host. Generally, electrochemical oxidation did not significantly alter the slow rate of ferrocene guest dissociation or release from the hemicarceplexes surveyed.

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“…compound with a known X-ray crystal structure similar to the PVF films in this case ferrocenium hexafluorophosphate (FcPF6) [12] are shown in Fig. 1.…”

Section: Xas Measurements Of the Model Compound Amentioning

confidence: 98%

“…The fitting was done using single scattering and the results are summarised in Table 1. The results obtained for the FcPF 6 aNeed with the X-ray data reported previously [12] and was used as reference for the simulation of the PVF samples. The Rfactor, R, is the residual from the difference between experimental and theoretical spectra.…”

Section: Xas Measurements Of the Model Compound Amentioning

confidence: 99%

Combined XAS/SAXS/Electrochemical studies on the conformation of poly(vinylferrocene) under redox conditions

Schlindwein

Kavvada

Linford

et al. 2002

Ionics

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Abstract. Metal-organic ligand complexes are important to many processes, ranging from the formation of supramolecular assemblies to electrochemical processes. Poly(vinylferrocene), PVF, is an example of a metal-organic polymer that contains localised sites which may be oxidised and reduced. Combined XAS (X-ray Absorption Spectroscopy) / SAXS (Small Angle X-ray Scattering) and electrochemical studies on PVF films in aqueous solution of 0.10 M LiCIO4 and in nonaqueous solution of propylene carbonate/0.25 M TBABF 4 have been carried out. The change in the oxidation Fe2 § of the PVF film was observed by analysing the near edge region of the XAS spectrum. The local environment around the Fe-centres of the oxidised/reduced films (from the extended region of the XAS spectrum) indicates an increase/reduction of ligand distances during the oxidation and reduction of the film. The SAXS results correlate well with the findings from XAS. The scattering profiles at very low angles are consistent with an expansion/contraction of the overall size of polymer chains upon oxidation/reduction.

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Structure of ferrocenium hexafluorophosphate

Abstract: reflections. The structure consists of a PF~-anion in a general position and two ferrocenium cations lying on independent crystallographic inversion centres. This imposed symmetry leads to the cyclopentadienyl rings being ideally staggered (twist angle 36 ° from eclipsed conformation).

Cited by 40 publications

References 10 publications

One electron oxidation of triferrocenylmethanol: synthesis, metal atom dynamics, electron delocalization, and the crystal structure of [Fc3COH]+ PF6−

One electron oxidation of triferrocenylmethanol: synthesis, metal atom dynamics, electron delocalization, and the crystal structure of [Fc3COH]+ PF6−

Electrochemistry of Encapsulated Guests: Ferrocene inside Cram's Hemicarcerands

Combined XAS/SAXS/Electrochemical studies on the conformation of poly(vinylferrocene) under redox conditions

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