Preparation and structural characterisation of a novel ferrocene-amino acid conjugate

Inorganic Chemistry Communications

Volumn 13, Issue 1, 2010, Pages 149-152

  Tauchman, Jiří ^a   Štěpnička, Petr ^a  

^a CHARLES UNIVERSITY   (Czech Republic)

Author keywords

Cyclic voltammetry; Ferrocene; Ferrocenophane; Glycine; Structure elucidation

Indexed keywords

EID: 72249110465     PISSN: 13877003     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.inoche.2009.10.038     Document Type: Article

References (28)

1. Metzler-Nolte N., and Salmain M. The bioorganometallic chemistry of ferrocene. In: Štěpnička P. (Ed). Ferrocenes: Ligands, Materials and Biomolecules (2008), Wiley, Chichester 499-639 (Chapter 13)
2. Moriuchi T., and Hirao T. Top. Organomet. Chem. 17 (2006) 143
3. Kraatz H.-B. J. Inorg. Organomet. Polym. Mater. 15 (2005) 83
4. van Staveren D.R., and Metzler-Nolte N. Chem. Rev. 104 (2004) 5931
5. Moriuchi T., and Hirao T. Chem. Soc. Rev. 33 (2004) 294
6. Lorkowski H.-J., and Kieselack P. Chem. Ber. 99 (1966) 3619
7. Georgopoulou A.S., Mingos D.M.P., White A.J.P., Williams D.J., Horrocks B.R., and Houlton A. J. Chem. Soc., Dalton Trans. (2000) 2969
8. Plenio H., Yang J., Diodone R., and Heinze J. Inorg. Chem. 33 (1994) 4098
9. N'Diaye C.M., Maciejewski L.A., Brocard J.S., and Biot C. Tetrahedron Lett. 42 (2001) 7221
10. Osakada K., Sakano T., Horie M., and Suzaki Y. Coord. Chem. Rev. 250 (2006) 1012 and references cited therein
11. Synthesis of a ferrocenophane-based γ-amino acid has been recently communicated by Erker and coworkers:. Tebben L., Bussmann K., Hegemann M., Kehr G., Fröhlich R., and Erker G. Organometallics 27 (2008) 4269
12. 2Me]Cl (110 mg, 0.88 mmol). After stirring at room temperature under Ar atmosphere for 5 min, triethylamine (0.2 mL, 1.76 mmol) was introduced and the mixture was heated at 170 °C in the dark for 24 h. Then, the volatiles were removed under vacuum and the dark residue was extracted with ethyl acetate. Some insoluble by-products were separated by filtration and the extract was purified by column chromatography (silica gel, hexane:ethyl acetate, 5:1 v/v). The second band was collected and evaporated to afford analytically pure 1 as a yellow solid (24 mg, 10%). The first minor band contains mostly 2-oxa[3]ferrocenophane according to NMR spectra [9].
13. Carroll M.A., White A.J.P., Widdowson D.A., and Williams D.J. J. Chem. Soc., Perkin Trans. 1 (2000) 1551
14. Aggarwal V.K., Jones D., Turner M.L., and Adams H. J. Organomet. Chem. 524 (1996) 263
15. Glycine methyl ester is formed in situ from glycine methyl ester hydrochloride and triethylamine.
16. 2: C, 60.22; H, 5.73; N, 4.68%. Found: C, 60.00; H, 5.61; N, 4.57%.
17. -3.
18. Altomare A., Burla M.C., Camalli M., Cascarano G.L., Giacovazzo C., Guagliardi A., Moliterni A.G.G., Polidori G., and Spagna R. J. Appl. Crystallogr. 32 (1999) 115
19. G.M. Sheldrick, Shelxl97, Program for Crystal Structure Refinement from Diffraction Data, University of Göttingen, Germany, 1997.
20. Atoms defining the {C13, C14, O1, O2, C15} plane are coplanar within 0.01 Å.
21. Unchanged 1 was recovered after reacting with an excess of MeI in acetonitrile overnight (5 mg (17 μmol) of 1 and 14 mg (0.1 mmol) of MeI in 1 mL of dry solvent).
22. Compound 1 (5 mg, 17 μmol) and 2,4,6-trinitrophenol (Hpic; 4.5 mg, 20 μmol) were dissolved in ethyl acetate (1 mL). The mixture was layered with hexane (2 mL) and allowed to crystallise at room temperature. The separated deep red crystalline picrate 2 was filtered off, washed with pentane and dried under vacuum. The yield was not determined.
23. -1.
24. For recent references dealing with IR spectra of amino acid picrates, see:. Mary M.B., Sasirekha V., and Ramakrishnan V. Spectrochim. Acta Part A 65 (2006) 414
25. Senthilkumar S., Mary M.B., and Ramakrishnan V. J. Raman Spectrosc. 38 (2007) 288
26. 6] (Fluka, puriss. for electrochemistry). The solutions were deaerated with argon prior to the measurement and then kept under an argon blanket. The redox potentials are given relative to ferrocene/ferrocenium reference. Reactions with HCl and MeI were performed directly in the cell. The reagents were added to the analysed solution (0.7 M HCl in MeOH, neat MeI) and the mixture was stirred for 5 (HCl) or 30 min (MeI) to ensure complete reaction.
27. -1) was close to that of ferrocene itself under the same conditions (ca. 70 mV).
28. Some ill-defined peaks were observed in the cathodic region of the voltammogram.