Metal atom dynamics in organometallics: Vibrational amplitude determination for bis phosphino ferrocenes including a waxy system

Herber, Rolfe H.; Nowik, I.

doi:10.1016/j.jorganchem.2008.06.017

Cited by 14 publications

(2 citation statements)

References 15 publications

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“…With respect to the dynamical parameters extracted from the ME data it is noteworthy that the temperature dependence of the recoil-free fraction, as reflected in the area under the resonance curve, is much larger for 3a BPh 4 than for 2a , and this effect is also noted in a comparison of the lattice temperature, Θ M , for the two compounds. Since single-crystal X-ray data have been determined for both complexes, it is possible to calculate the root-mean-square amplitude of vibration (rmsav) of the metal atom from the crystallographic U i , j values and to compare these with the corresponding data extracted from the ME data, using the procedure detailed earlier . For 2a , these values at 120 K are F x,120 = 0.64 ± 0.05 and F M,120 = 0.68 ± 0.06.…”

Section: Resultsmentioning

confidence: 99%

Ferracarborane Benzene Complexes [(η-9-L-7,8-C₂B₉H₁₀)Fe(η-C₆H₆)]⁺ (L = SMe₂, NMe₃): Synthesis, Reactivity, Electrochemistry, Mössbauer Effect Studies, and Bonding

et al. 2010

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The benzene complexes [(η-9-L-7,8-C2B9R2H8)Fe(η-C6H6)]+ (3a: L = SMe2, R = H; 3b: L = SMe2, R = Me; 3c: L = NMe3, R = H) were prepared by photochemical reaction of [(η5-C6H7)Fe(η-C6H6)]+ with carborane anions [9-L-7,8-C2B9R2H8]− (1a−c) followed by treatment of the (η-9-L-7,8-C2B9R2H8)Fe(η5-C6H7) (2a−c) ferracarboranes formed with HCl. Visible light irradiation of 3a with t BuNC or P(OMe)3 in acetonitrile results in replacement of the benzene ligand, giving the tris(ligand) derivatives [(η-9-SMe2-7,8-C2B9H10)Fe(ligand)3]+ (4, 5). The unsymmetrical carborane complex (η-9-SMe2-7,8-C2B9H10)Fe(η-9-NMe3-7,8-C2B9H10) (6) was obtained by photochemical reaction of 3a with 1c. The structures of 2a, 3aBPh4, and 6 were determined by X-ray diffraction. Temperature-dependent Mössbauer spectroscopy has been used to elucidate the hyperfine parameters and metal atom vibrational amplitudes in a number of these complexes. The redox activity of the ferracarboranes 2a,c and 3a,c has been investigated by electrochemical techniques and compared with that of the related cyclopentadienyl complexes. Electrochemistry gives evidence that the conversion of 2a−c to 3a−c can also be triggered by a two-electron oxidation followed by deprotonation. DFT calculations of the redox potentials and the respective geometrical changes were performed. Data on electrostatic potentials at iron nuclei suggest that anions 1a,c are stronger donors than Cp− in cationic complexes, but weaker donors in the neutral derivatives.

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Section: Resultsmentioning

confidence: 99%

Ferracarborane Benzene Complexes [(η-9-L-7,8-C₂B₉H₁₀)Fe(η-C₆H₆)]⁺ (L = SMe₂, NMe₃): Synthesis, Reactivity, Electrochemistry, Mössbauer Effect Studies, and Bonding

et al. 2010

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“…Temperature-dependent Mössbauer experiments were carried out as previously described [ 21 ], using a 57 Co(Rh) source in transmission geometry. Spectrometer calibration was effected using a 20 mg cm −2 α-Fe absorber at room temperature, and all isomer shifts are referred to the centroid of such spectra.…”

Section: Methodsmentioning

confidence: 99%

Mössbauer Spectroscopy and X-ray Diffraction Study of 57Fe-Labeled Tetrachloroferrate(III)-Based Magnetic Ionic Liquids

Herber

Nowik

Kostner

et al. 2011

IJMS

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Four 57Fe-labeled tetrachloroferrates(III) of organic cations (1-butyl-3-methylimidazolium, 1-allyl-3-methylimidazolium, 1-methyl-1-propylpyrrolidinium, tetraphenylphosphonium) were examined by temperature-dependent Mössbauer spectroscopy. The hyperfine and dynamic parameters of the iron(III) site were determined. Single crystal X-ray diffraction data of [Ph4P][FeCl4] were collected at four temperatures (295, 223, 173, and 123 K), and the dynamics of the iron atom inferred from the Mössbauer data and the single crystal Ui,j parameters have been compared.

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Ionic Liquids of Cationic Sandwich Complexes

Inagaki

Mochida

Takahashi

et al. 2012

Chemistry A European J

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Simple cationic sandwich complexes that contained alkyl- or halogen substituents provided ionic liquids (ILs) with the bis(perfluoroalkanesulfonyl)imide anion. Ferrocenium- and cobaltocenium ILs [M(C(5)H(4)R(1))(C(5)H(4)R(2))][Tf(2)N] (M=Fe, Co) and arene-ferrocenium ILs [Fe(C(5)H(4)R(1))(C(6)H(5)R(2))][Tf(2)N] were prepared and their physical properties were investigated. A detailed comparison of their thermal properties revealed the effects of molecular symmetry and substituents on their melting points. Their viscosity increased on increasing the length of the substituent on the cation and the perfluoroalkyl chain length on the anion. Upon cooling, ILs with low viscosities exhibited crystallization, whereas those with higher viscosities tended to exhibit glass transitions. Most of these salts showed phase transitions in the solid state. A magnetic-switching phenomenon was observed for the paramagnetic ferrocenium IL, which was associated with a liquid/solid transformation, based on the magnetic anisotropy of the ferrocenium cation. (57)Fe Mössbauer spectroscopy was applied to [Fe(C(5)H(4)nBu)(2)][Tf(2)N] to investigate the vibrational behavior of the iron atom in the crystal and glassy states of the ferrocenium IL.

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Metal atom dynamics in organometallics: Vibrational amplitude determination for bis phosphino ferrocenes including a waxy system

Cited by 14 publications

References 15 publications

Ferracarborane Benzene Complexes [(η-9-L-7,8-C₂B₉H₁₀)Fe(η-C₆H₆)]⁺ (L = SMe₂, NMe₃): Synthesis, Reactivity, Electrochemistry, Mössbauer Effect Studies, and Bonding

Ferracarborane Benzene Complexes [(η-9-L-7,8-C₂B₉H₁₀)Fe(η-C₆H₆)]⁺ (L = SMe₂, NMe₃): Synthesis, Reactivity, Electrochemistry, Mössbauer Effect Studies, and Bonding

Mössbauer Spectroscopy and X-ray Diffraction Study of 57Fe-Labeled Tetrachloroferrate(III)-Based Magnetic Ionic Liquids

Ionic Liquids of Cationic Sandwich Complexes

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Metal atom dynamics in organometallics: Vibrational amplitude determination for bis phosphino ferrocenes including a waxy system

Cited by 14 publications

References 15 publications

Ferracarborane Benzene Complexes [(η-9-L-7,8-C2B9H10)Fe(η-C6H6)]+ (L = SMe2, NMe3): Synthesis, Reactivity, Electrochemistry, Mössbauer Effect Studies, and Bonding

Ferracarborane Benzene Complexes [(η-9-L-7,8-C2B9H10)Fe(η-C6H6)]+ (L = SMe2, NMe3): Synthesis, Reactivity, Electrochemistry, Mössbauer Effect Studies, and Bonding

Mössbauer Spectroscopy and X-ray Diffraction Study of 57Fe-Labeled Tetrachloroferrate(III)-Based Magnetic Ionic Liquids

Ionic Liquids of Cationic Sandwich Complexes

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Product

Resources

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Ferracarborane Benzene Complexes [(η-9-L-7,8-C₂B₉H₁₀)Fe(η-C₆H₆)]⁺ (L = SMe₂, NMe₃): Synthesis, Reactivity, Electrochemistry, Mössbauer Effect Studies, and Bonding

Ferracarborane Benzene Complexes [(η-9-L-7,8-C₂B₉H₁₀)Fe(η-C₆H₆)]⁺ (L = SMe₂, NMe₃): Synthesis, Reactivity, Electrochemistry, Mössbauer Effect Studies, and Bonding