Bonding, hyperfine interactions, and lattice dynamics of bis(pentadienyl)iron compounds

Ernst, Richard D.; Wilson, David R.; Herber, R. H.

doi:10.1021/ja00318a017

Cited by 57 publications

(20 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The 57 Fe Mößbauer spectroscopic data of 1 TMS Sn are indicative of an unperturbed ferrocene‐type iron(II) species. The spectrum shows a doublet (Δ E Q =2.31(1) mm s −1 ) with an isomer shift of δ =0.41(1) mm s −1 at 5 K. For comparison, the values reported for pristine ferrocene are δ =0.41(1) mm s −1 and Δ E Q =2.34 mm s −1 . The 57 Fe Mößbauer spectroscopic signature of the potential contaminant 1 TMS H 2 (hydrolysis product of 1 TMS Sn) is distinguishable from the stannylene 1 TMS Sn, although the fitting parameters of both compounds, as expected, are quite similar.…”

Section: Resultsmentioning

confidence: 88%

Redox‐Active N‐Heterocyclic Germylenes and Stannylenes with a Ferrocene‐1,1′‐diyl Backbone

Oetzel

Weyer

Bruhn

et al. 2016

Chemistry A European J

View full text Add to dashboard Cite

We describe ferrocene-based N-heterocyclic germylenes and stannylenes of the type [Fe{(η -C H )NR} E:] (1 RE; E=Ge, Sn; R=neopentyl (Np), mesityl (Mes), trimethylsilyl (TMS)), which constitute the first examples of redox-functionalised N-heterocyclic tetrylenes (NHTs). These compounds are thermally stable and were structurally characterised by means of X-ray diffraction studies, except for the neopentyl-substituted stannylene 1 NpSn, the decomposition of which afforded the aminoiminoferrocene [fc(NHCH tBu)(N=CHtBu)] (2) and the spiro tin(IV) compound (1 Np) Sn (3). DFT calculations show that the HOMO of the NHTs of our study is localised on the ferrocenylene backbone. A one-electron oxidation process affords ions of the type 1 RE . In contrast to the NHC system 1 RC, the localised ferrocenium-type nature of the oxidised form does not compromise the fundamental tetrylene character of 1 RE .

show abstract

Section: Resultsmentioning

confidence: 88%

Redox‐Active N‐Heterocyclic Germylenes and Stannylenes with a Ferrocene‐1,1′‐diyl Backbone

Oetzel

Weyer

Bruhn

et al. 2016

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…The temperature dependence of the isomer shift of amorphous iron, although admittedly based on only two data points, yields 24 an effective recoil mass M eff of 70 g/mol, a value that is larger than the value of 65 g/mol observed 25 for ␣-iron. This increase in effective recoil mass results from the decreased number of near neighbors and the corresponding increase in the covalency of the bonding in amorphous iron as compared to ␣-iron.…”

Section: A Mössbauer Spectramentioning

confidence: 75%

“…This increase in effective recoil mass results from the decreased number of near neighbors and the corresponding increase in the covalency of the bonding in amorphous iron as compared to ␣-iron. The temperature dependence of the isomer shift and the absolute spectral absorption area yield 24 the effective Mössbauer temperature, M , a quantity that is similar to the Debye temperature. The observed value of 377 K is somewhat larger than the value of 345 K observed 26,27 for nanostructured iron but is, as expected, substantially lower than the value of ca.…”

Section: A Mössbauer Spectramentioning

confidence: 99%

Mössbauer-effect and x-ray-absorption spectral study of sonochemically prepared amorphous iron

et al. 1998

View full text Add to dashboard Cite

The Mössbauer spectra of amorphous iron, prepared by using sonochemical methods, exhibit a broad magnetic hyperfine sextet at both 78 and 295 K. The spectra do not change with time if the amorphous iron is not exposed to oxygen or moisture. An analysis of the spectra with the method of Lines and Eibschütz yields average magnetic hyperfine fields of 29.1 and 25.9 T at 78 and 295 K, respectively. The corresponding moments of 1.9 B and 1.7 B agree well with values obtained from earlier magnetization studies and, further, provide strong experimental support for earlier calculations of the magnetic moments in amorphous iron. The observed average isomer shifts of 0.27 and 0.14 mm/s obtained at 78 and 295 K, respectively, correspond to a decrease in the s-electron density at the iron-57 nucleus as compared to that of ␣-iron, a decrease which is consistent with the decreased coordination number of amorphous iron. The similarity of the 295 K iron K-edge x-ray-absorption spectrum of amorphous iron and ␣-iron, up to 7130 eV, indicates that the d-electron density of states just above the Fermi level is similar in both forms of iron. The absence of structural details above 7130 eV in the spectrum of amorphous iron indicates, in agreement with multiple-scattering calculations, that long-range order does not extend beyond the third shell of neighbors in amorphous iron. Greatly reduced extended x-ray-absorption-fine-structure scattering is observed at the iron K edge of amorphous iron as compared to ␣-iron. An analysis of the weak observed scattering reveals both a decrease in the average coordination number from 14 in ␣-iron to 10 in amorphous iron, and an asymmetric radial distribution function of the iron neighbors in the first shell. This asymmetric distribution yields for amorphous iron a minimum iron-iron distance of 2.40 Å and an average iron-iron distance of 2.92 Å. ͓S0163-1829͑98͒08817-1͔

show abstract

“…Although based on only two data points, and thus less reliable, the lattice properties of the three sites seem reasonable. The temperature dependence of the isomer shifts yields (33) effective recoil masses of 64, 56, and 110 g/mol for the Fe(1), Fe(2), and Fe(3) sites, respectively. The values for the Fe(1) and Fe(2) sites are very typical for ionic iron oxides and indeed the value for the Fe(1) site, with the shorter average bond distance, has the higher mass.…”

Section: Structural Descriptionmentioning

confidence: 99%

Hydrothermal Synthesis, Structure, and Characterization of a Mixed-Valent Iron(II/III) Phosphate, NaFe3.67(PO4)3: A New Variation of the Alluaudite Structure Type

Korzenski

Schimek

Kolis

et al. 1998

Journal of Solid State Chemistry

View full text Add to dashboard Cite

Bonding, hyperfine interactions, and lattice dynamics of bis(pentadienyl)iron compounds

Cited by 57 publications

References 0 publications

Redox‐Active N‐Heterocyclic Germylenes and Stannylenes with a Ferrocene‐1,1′‐diyl Backbone

Redox‐Active N‐Heterocyclic Germylenes and Stannylenes with a Ferrocene‐1,1′‐diyl Backbone

Mössbauer-effect and x-ray-absorption spectral study of sonochemically prepared amorphous iron

Hydrothermal Synthesis, Structure, and Characterization of a Mixed-Valent Iron(II/III) Phosphate, NaFe3.67(PO4)3: A New Variation of the Alluaudite Structure Type

Contact Info

Product

Resources

About