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[3]Ferrocenophanes with a tetramethyldisiloxane bridge: Synthesis and molecular structure

[3]Ferrocenophane mit Tetramethyldisiloxan-Brücke: Synthese und Molekülstruktur

  • Organische Chemie Und Biochemie
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Summary

6,6,8,8-Tetramethyl-7-oxa-6,8-disila[3]ferrocenophane2 was obtained from the di(alkoxysilyl) ferrocene (H4C5SiMe2OR)2Fe (R=CH2CH2OCH2CH2OCH2CH2OMe) by hydrolysis and subsequent intramolecular disiloxane formation. 2,2′,3,3′,4,4′,5,5′,6,6,8,8-Dodecamethyl-7-oxa-6,8-disila-[3]ferrocenophane3 was formed by air oxidation of 2,2′3,3′,4,4′,5,5′,6,6,7,7-dodecamethyl-6,7-disila[2]ferrocenophane. The crystal structures of both compounds were determined by single-crystal X-ray diffraction (2:a=8.5330(10),b=15.610(3),c=18.774(5)Å, α=70.68(2), β=77.94(2), γ=75.150(10)°,V=2259.8(8)Å3,Z=6, space group P\(\bar 1\),R=0.045,R w =0.044;3:a=12.388(3),b=9.924(3),c=19.136(10)Å, β=105.11(3)°,V=2271.2(15)Å3,Z=4, space group P21/c,R=0.076,R w =0.060). Owing to the flexibility of the disiloxane bridge,2 and3 are unstrained molecules.

Zusammenfassung

6,6,8,8-Tetramethyl-7-oxa-6,8-disila[3]-ferrocenophan2 entsteht aus dem Di(alkoxysilyl)ferrocen (H4C5SiMe2OR)2Fe (R=CH2CH2OCH2CH2OCH2CH2OMe) durch Hydrolyse und anschließende intramolekulare Disiloxan-Bildung. 2,2′,3,3′,4,4′,5,5′,6,6,8,8-Dodecamethyl-7-oxa-6,8-disila[3]ferrocenophan3 wurde durch Luftoxidation von 2,2′,3,3′,4,4′,5,5′,6,6,7,7-Dodecamethyl-6,7-disila[2]ferrocenophan erhaeten. Die Kristallstrukturen beider Verbindungen wurden durch Einkristall-Röntgenstrukturanalyse bestimmt (2:a=8.5330(10),b=15.610(3),c=18.774(5)Å, α=70.68(2), β=77.94(2), γ=75.150(10)°,V=2259.8(8)Å3,Z=6, Raumgruppe P\(\bar 1\),R=0.045,R w =0.044;3:a=12.388(3),b=9.924(3),c=19.136(10)Å, β=105.11(3)°,V=2271.2(15)Å3,Z=4, Raumgruppe P21/c,R=0.076,R w =0.060). Wegen der Flexibilität der Disiloxan-Brücke sind2 und3 ungespannte Moleküle.

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References

  1. Hisatome M., Watanabe J., Kawajiri Y., Yamakawa K. (1990) Organometallics9: 497

    Google Scholar 

  2. See, for example: Herberhold M., Leitner P., Thewalt U. (1990) Z. Naturforsch.45b: 1503; Herberhold M., Leitner P. (1991) J. Organomet. Chem.411: 233; Herberhold M., Dörnhöfer C., Scholz A., Jin G.-X. (1992) Phosphorus Sulfur Silicon Relat. Elem.64: 161; Zanello P., Opromolla G., Casarin M., Herberhold M., Leitner P. (1993) J. Organomet. Chem.443: 199

    Google Scholar 

  3. Siemeling U., Neumann B., Stammler H.-G. (1993) Chem. Ber.126: 1311

    Google Scholar 

  4. The synthesis of2 was reported as early as 1961 by Schaaf et al. using a strategy similar to ours: Schaaf R. L., Kan P. T., Lenk C. T. (1961) J. Org. Chem.26: 1790

    Google Scholar 

  5. It is well known that strained disilanes can react with dioxygen to give disiloxanes; see, for example: Atwell W. H., Uhlmann J. G. (1973) J. Organomet. Chem.52: C21; Seyferth D., Vick S. C. (1977) J. Organomet. Chem.125: C11; Sakurai H., Kobayashi T., Nakadaira Y. (1978) J. Organomet. Chem.162: C43

    Google Scholar 

  6. Krallmann R. (1991) Thesis, Bielefeld, p. 158

  7. It cannot be ruled out that ferrocenium ions participate in the reaction as catalyst: Tamao K., Kumada M., Takahashi T. (1975) J. Organomet. Chem.94: 367

    Google Scholar 

  8. Elschenbroich C., Salzer A. (1988) Organometallchemie, 2nd ed. Teubner, Stuttgart, p. 380; Freyberg D. P., Robbins J. L., Raymond K. N., Smart J. C. (1979) J. Am. Chem. Soc.101: 892

    Google Scholar 

  9. Wells A. F. (1991) Structural Inorganic Chemistry, 5th ed. (4th corr. repr.). Clarendon Press, Oxford, p. 1000

    Google Scholar 

  10. There has been some controversy about the reasons for this unusual behaviour; for a comprehensive discussion, see: Shambayati S., Blake J. F., Wierschke S. G., Jorgensen W. L., Schreiber S. L. (1990) J. Am. Chem. Soc.112: 697

    Google Scholar 

  11. Additional material to the structure determination can be ordered from Fachinformationszentrum Energie-Physik-Mathematik, D-76344 Eggenstein-Leopoldshafen, Federal Republic of Germany, referring to the deposition numbers CSD-57418, to the names of the authors and the citation of the paper.

  12. Ibers J. A., Hamilton W. C. (eds.) (1974) International Tables for X-ray Crystallography, Vol. IV. Kynoch Press, Birmingham

    Google Scholar 

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Authors and Affiliations

  1. Fakultät für Chemie, Universität Bielefeld, D-33615, Bielefeld, Germany

    U. Siemeling, R. Krallmann, P. Jutzi, B. Neumann & H. -G. Stammler

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  1. U. Siemeling
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  2. R. Krallmann
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  3. P. Jutzi
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  4. B. Neumann
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  5. H. -G. Stammler
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Siemeling, U., Krallmann, R., Jutzi, P. et al. [3]Ferrocenophanes with a tetramethyldisiloxane bridge: Synthesis and molecular structure. Monatsh Chem 125, 579–586 (1994). https://doi.org/10.1007/BF00811851

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