Multiferrocenyl Cobalt-Based Sandwich Compounds

Grzegorz Filipczyk, Steve W. Lehrich, Alexander Hildebrandt, Tobias Rueffer, Dieter Schaarschmidt, Marcus Korb, Heinrich Lang

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

The reaction of FcC=C-C=CFc [Fc = Fe(eta(5)-C5H4)(eta(5)-C5H5)] (1) with Co(eta(5)-C5H5)(CO)(2) (2) afforded ferrocenyl-functionalized cyclobutadiene and cyclopentadienone cobalt(I) compounds as well as multiferrocenyl benzene derivatives. The synthesis procedures are described. Eleven products could be separated by column chromatography and were characterized by NMR, UV/Vis, and IR spectroscopy, high-resolution ESI-TOF mass spectrometry and elemental analysis. For five representatives, the structure in the solid state was determined by single X-ray structure analysis. The electronic properties of the appropriate compounds were studied by using cyclic and square-wave voltammetry. Further investigation of the interaction between Fe-II/Fe-III centers in the mixed-valent species was achieved by in situ UV/Vis/NIR spectroelectrochemistry. These measurements demonstrated that weak electronic metal-metal interactions through the cobalt-coordinated cyclobutadiene building block occur (weakly coupled class II systems according to the classification of Robin and Day), whereas the cyclopentadienone core acts as an insulator (class I), and hence only electrostatic interactions are characteristic.

Original languageEnglish
Pages (from-to)263-275
Number of pages13
JournalEuropean Journal of Inorganic Chemistry
Issue number2
DOIs
Publication statusPublished - Jan 2017
Externally publishedYes

Cite this

Filipczyk, G., Lehrich, S. W., Hildebrandt, A., Rueffer, T., Schaarschmidt, D., Korb, M., & Lang, H. (2017). Multiferrocenyl Cobalt-Based Sandwich Compounds. European Journal of Inorganic Chemistry, (2), 263-275. https://doi.org/10.1002/ejic.201600848
Filipczyk, Grzegorz ; Lehrich, Steve W. ; Hildebrandt, Alexander ; Rueffer, Tobias ; Schaarschmidt, Dieter ; Korb, Marcus ; Lang, Heinrich. / Multiferrocenyl Cobalt-Based Sandwich Compounds. In: European Journal of Inorganic Chemistry. 2017 ; No. 2. pp. 263-275.
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Filipczyk, G, Lehrich, SW, Hildebrandt, A, Rueffer, T, Schaarschmidt, D, Korb, M & Lang, H 2017, 'Multiferrocenyl Cobalt-Based Sandwich Compounds' European Journal of Inorganic Chemistry, no. 2, pp. 263-275. https://doi.org/10.1002/ejic.201600848

Multiferrocenyl Cobalt-Based Sandwich Compounds. / Filipczyk, Grzegorz; Lehrich, Steve W.; Hildebrandt, Alexander; Rueffer, Tobias; Schaarschmidt, Dieter; Korb, Marcus; Lang, Heinrich.

In: European Journal of Inorganic Chemistry, No. 2, 01.2017, p. 263-275.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Multiferrocenyl Cobalt-Based Sandwich Compounds

AU - Filipczyk, Grzegorz

AU - Lehrich, Steve W.

AU - Hildebrandt, Alexander

AU - Rueffer, Tobias

AU - Schaarschmidt, Dieter

AU - Korb, Marcus

AU - Lang, Heinrich

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N2 - The reaction of FcC=C-C=CFc [Fc = Fe(eta(5)-C5H4)(eta(5)-C5H5)] (1) with Co(eta(5)-C5H5)(CO)(2) (2) afforded ferrocenyl-functionalized cyclobutadiene and cyclopentadienone cobalt(I) compounds as well as multiferrocenyl benzene derivatives. The synthesis procedures are described. Eleven products could be separated by column chromatography and were characterized by NMR, UV/Vis, and IR spectroscopy, high-resolution ESI-TOF mass spectrometry and elemental analysis. For five representatives, the structure in the solid state was determined by single X-ray structure analysis. The electronic properties of the appropriate compounds were studied by using cyclic and square-wave voltammetry. Further investigation of the interaction between Fe-II/Fe-III centers in the mixed-valent species was achieved by in situ UV/Vis/NIR spectroelectrochemistry. These measurements demonstrated that weak electronic metal-metal interactions through the cobalt-coordinated cyclobutadiene building block occur (weakly coupled class II systems according to the classification of Robin and Day), whereas the cyclopentadienone core acts as an insulator (class I), and hence only electrostatic interactions are characteristic.

AB - The reaction of FcC=C-C=CFc [Fc = Fe(eta(5)-C5H4)(eta(5)-C5H5)] (1) with Co(eta(5)-C5H5)(CO)(2) (2) afforded ferrocenyl-functionalized cyclobutadiene and cyclopentadienone cobalt(I) compounds as well as multiferrocenyl benzene derivatives. The synthesis procedures are described. Eleven products could be separated by column chromatography and were characterized by NMR, UV/Vis, and IR spectroscopy, high-resolution ESI-TOF mass spectrometry and elemental analysis. For five representatives, the structure in the solid state was determined by single X-ray structure analysis. The electronic properties of the appropriate compounds were studied by using cyclic and square-wave voltammetry. Further investigation of the interaction between Fe-II/Fe-III centers in the mixed-valent species was achieved by in situ UV/Vis/NIR spectroelectrochemistry. These measurements demonstrated that weak electronic metal-metal interactions through the cobalt-coordinated cyclobutadiene building block occur (weakly coupled class II systems according to the classification of Robin and Day), whereas the cyclopentadienone core acts as an insulator (class I), and hence only electrostatic interactions are characteristic.

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KW - Cobalt

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KW - UNSATURATED HYDROCARBON BRIDGES

KW - CHARGE-TRANSFER PROPERTIES

KW - QUANTUM CELLULAR-AUTOMATA

KW - WAVE POTENTIAL SPLITTINGS

KW - METAL-METAL INTERACTIONS

KW - MOLECULAR ELECTRONICS

KW - ORGANOMETALLIC COMPLEXES

KW - 5-MEMBERED HETEROCYCLES

KW - NONAQUEOUS SOLVENTS

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DO - 10.1002/ejic.201600848

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JO - European Journal of Inorganic Chemistry

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SN - 1099-0682

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Filipczyk G, Lehrich SW, Hildebrandt A, Rueffer T, Schaarschmidt D, Korb M et al. Multiferrocenyl Cobalt-Based Sandwich Compounds. European Journal of Inorganic Chemistry. 2017 Jan;(2):263-275. https://doi.org/10.1002/ejic.201600848