A M�ssbauer study of some ferrocene derivatives

Stukan, R. A.; Губин, С. П.; Nesmeyanov, A. N.; Goldanskii, V. I.; Makarov, E. F.

doi:10.1007/bf01000961

Cited by 16 publications

(12 citation statements)

References 9 publications

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“…In the case of the Fctpy, a wide doublet peak with QS (quadrupole splitting) = 2.33 mm s −1 and IS = 0.45 mm s −1 was observed; these values correspond to those reported for (diamagnetic) pristine ferrocene. 29 We observed similar wide doublet peaks for 1 (QS = 1.92 mm s −1 , IS = 0.39 mm s −1 ) and 5 (QS = 1.86 mm s −1 , IS = 0.38 mm s −1 ), respectively, demonstrating that the ferrocene substituent remained intact after the oxidation of the cobalt(II) to cobalt(III) had occurred in 1.…”

Section: Dalton Transactions Papersupporting

confidence: 59%

Redox induced colour changes between red-violet and blue in hetero-metal complexes of the type [Co^II(4′-ferrocenyl-2,2′;6′2′′-terpyridine)₂]X₂ (X = counter anion)

et al. 2015

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The hetero-metal complexes [Co(II)(Fctpy)2]X2 (Fctpy = 4'-ferrocenyl-2,2';6'2''-terpyridine, X = PF6 (1), BF4 (2), ClO4 (3), BPh4 (4)) were prepared and their structures and properties were investigated by single crystal X-ray structural analysis, cyclic voltammetry, Mössbauer spectroscopy, UV-vis spectroscopy measurements and DFT calculations. These compounds show reversible redox behaviour in the solid state and switching of the colour between red-violet and blue in response to the change of the oxidation state of the cobalt ion centres. [Co(II)(Fctpy)2](PF6)2 (1) and [Co(III)(Fctpy)2](PF6)3 (5) were isolated as the red and blue crystalline products, and the crystal structures were determined. From the results of UV-vis spectroscopy and the DFT calculations, we assigned the respective colours as resulting from MLCT involving the ferrocenyl substituents, with the shift in the wavelength of the MLCT reflecting the respective HOMO/LUMO stabilizations induced by the change in the oxidation state of the cobalt centres. Furthermore, these compounds 1-4 also showed counter anion-dependent spin crossover behaviours.

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Section: Dalton Transactions Papersupporting

confidence: 59%

Redox induced colour changes between red-violet and blue in hetero-metal complexes of the type [Co^II(4′-ferrocenyl-2,2′;6′2′′-terpyridine)₂]X₂ (X = counter anion)

et al. 2015

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“…In the case of the 57 Fe Mössbauer data both spectra could be reproduced well with single signals at isomer shifts of δ = 0.48(1) mms –1 ( 1 ) and δ = 0.45(1) mms –1 ( 2 ), the typical doublet spectra for diamagnetic low-spin Fe(II), S = 0. The isomer shifts and quadrupole splitting values of 1 and 2 are almost equal, indicating comparable 4s electron densities at the iron nuclei and lie in the range typical for substituted and unsubstituted ferrocene-based coordination compounds. − …”

Section: Resultsmentioning

confidence: 89%

Cyclic Distannene or Bis(stannylene) with a Ferrocenyl Backbone: Synthesis, Structure, and Coordination Chemistry

et al. 2018

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1,1'-Dilithioferrocene was reacted with 2 equiv of isopropyl (Ar*) or methyl (Ar') substituted terphenyl tin(II) chloride. Reaction product 1, carrying the bulkier terphenyl substituent Ar*, displays a bis(stannylene) structure in the solid state without formation of a tin-tin bond. Temperature-dependent solution Sn NMR spectroscopy, however, revealed a dynamic interplay between bis(stannylene) (100 °C) and cyclic distannene (-80 °C). In contrast to 1, the less bulky Ar' substituent results in a cyclic distannene 2. On the basis of temperature-dependentSn NMR spectroscopy the Sn-Sn bond of compound 2 was preserved up to 100 °C. Both compounds were further characterized by solid-state Sn NMR spectroscopy as well asSn and Fe Mössbauer spectroscopy. 1 reacted as a chelating ligand with nickel and palladium complexes [Ni(cod)] and [Pd(nbe)] (nbe = norbornene). In the resulting coordination compounds the nonstabilized stannylene acts as a donor as well as an acceptor ligand and shows a dynamic switch from donor to acceptor behavior in the monopalladium complex.

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“…The isomer shift quantifies electron density at the 57 Fe nuclei, and hence can be used to identify oxidation state; unfortunately, the isomer shifts in ferrocene (δ≈ 0.45-0.6) 39 , 40 and associated cations (δ≈ 0.51 – 0.62 for 1+ 41 , δ≈ 0.59 mm/sec for 2+ 10 ) are similar. The isomer shift range of previously reported formally Fe 1+ sandwich complexes (~0.52 – 0.73 at 77 K) 23 , 24 , 38 , 42 are smaller than that observed for 5 , but these literature examples almost exclusively exhibit low spin ground states; herein, we propose that 5 has a formal 4s 0 3d 7 high spin ground state with a reduced Fe spin population of +2.82 (see below).…”

Section: Resultsmentioning

confidence: 99%

Isolation and electronic structures of derivatized manganocene, ferrocene and cobaltocene anions

et al. 2020

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The discovery of ferrocene nearly 70 years ago marked the genesis of metallocene chemistry; although the ferrocenium cation was discovered soon afterwards, a derivatized ferrocenium dication was only isolated in 2016 and the monoanion of ferrocene has only been observed in low temperature electrochemical studies. Here we report the isolation of a derivatized ferrocene anion in the solid state as part of an isostructural family of 3 d metallocenates which consist of anionic complexes of a metal centre (manganese, iron or cobalt) sandwiched between two bulkyCp ttt ligands (where Cp ttt is {1,2,4-C 5 H 2 t Bu 3 }). These air- and thermally-sensitive complexes rapidly decompose above -30 °C, however, we were able to characterise all metallocenates by a wide range of physical techniques and ab initio calculations. These data have allowed us to map the electronic structures of this metallocenate family, including an unexpected high-spin S = 3/2 ground state for the 19e - derivatized ferrocene anion.

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A M�ssbauer study of some ferrocene derivatives

Cited by 16 publications

References 9 publications

Redox induced colour changes between red-violet and blue in hetero-metal complexes of the type [Co^II(4′-ferrocenyl-2,2′;6′2′′-terpyridine)₂]X₂ (X = counter anion)

Redox induced colour changes between red-violet and blue in hetero-metal complexes of the type [Co^II(4′-ferrocenyl-2,2′;6′2′′-terpyridine)₂]X₂ (X = counter anion)

Cyclic Distannene or Bis(stannylene) with a Ferrocenyl Backbone: Synthesis, Structure, and Coordination Chemistry

Isolation and electronic structures of derivatized manganocene, ferrocene and cobaltocene anions

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A M�ssbauer study of some ferrocene derivatives

Cited by 16 publications

References 9 publications

Redox induced colour changes between red-violet and blue in hetero-metal complexes of the type [CoII(4′-ferrocenyl-2,2′;6′2′′-terpyridine)2]X2 (X = counter anion)

Redox induced colour changes between red-violet and blue in hetero-metal complexes of the type [CoII(4′-ferrocenyl-2,2′;6′2′′-terpyridine)2]X2 (X = counter anion)

Cyclic Distannene or Bis(stannylene) with a Ferrocenyl Backbone: Synthesis, Structure, and Coordination Chemistry

Isolation and electronic structures of derivatized manganocene, ferrocene and cobaltocene anions

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Redox induced colour changes between red-violet and blue in hetero-metal complexes of the type [Co^II(4′-ferrocenyl-2,2′;6′2′′-terpyridine)₂]X₂ (X = counter anion)

Redox induced colour changes between red-violet and blue in hetero-metal complexes of the type [Co^II(4′-ferrocenyl-2,2′;6′2′′-terpyridine)₂]X₂ (X = counter anion)