Stabilization of Iron Clusters by Polyolato Ligands and Calcium Ions: An Fe14 Oxocluster from Aqueous Alkaline Solution

Angewandte Chemie (International Edition in English)

Volumn 36, Issue 7, 1997, Pages 776-779

  Burger, Joachim ^a   Klüfers, Peter ^a  

^a UNIVERSITY OF KARLSRUHE   (Germany)

Author keywords

Clusters; Erythritol; Iron; Magnetic properties; O ligands

Indexed keywords

EID: 0030742077     PISSN: 05700833     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.199707761     Document Type: Article

References (24)

1. G. R. Moore, Encyclopedia of Inorganic Chemistry, Vol. 4 (Ed.: R. B. King), Wiley, New York, 1994, pp. 1871-1883.
2. a) R. A. Eggleton, R. W. Fitzpatrick, Clays Clay Miner. 1988, 36, 111-124;
3. b) Q. A. Pankhurst, R. J. Pollard, ibid. 1992, 40, 268-272.
4. U. Schwertmann, R. M. Cornell, Iron Oxides in the Laboratory, VCH, Weinheim, 1991, p. 89.
5. W. Schneider, Comments Inorg. Chem. 1984, 3, 205-223.
6. J. Burger, P, Klüfers, Z. Anorg, Allg. Chem. 1996, 622, 1740-1748.
7. Neutralization of the solution led to a brown precipitate. After the suspension had been heated for two weeks at 98 °C and the precipitate subsequently dried at room temperature, the remaining solid was amorphous in terms of the X-ray scattering (Stoe powder diffractomer).
8. T. Aberle, W. Burchard, unpublished results.
9. 3. Geometrical analysis and drawings with PLATON and SCHAKAL, Further details of the crystal structure investigation may be obtained from the Fachinformationszentrum Karlsruhe, D-76344 Eggenstein-Leopoldshafen (Germany), on quoting the depository number CSD-405597.
10. The cluster cations combine to form a [00l]-elongated A2-type packing (W type, body-centered cubic packing), in which large voids occur around positions of the type 1/2, 0, 1/2. Electron density in these voids has been assigned to disordered formiate ions.
11. Compare with the isotypic phases ε-FeOOH and InOOH, which exhibit a rutile-type structure modified by hydrogen bonds: M. S. Lehmann, F. Krebs Larsen, F. Reibke Poulsen, A. Nørlund Christensen, S. E. Rasmussen, Acta Chem. Scand. 1970, 24, 1662-1670. The structural motif of four cyclically connected octahedra is also present in akaganéite, β-FeO(OH): P. Keller, Neues Jahrb. Miner. Ahh. 1970, 113, 29-49.
12. Compare with the isotypic phases ε-FeOOH and InOOH, which exhibit a rutile-type structure modified by hydrogen bonds: M. S. Lehmann, F. Krebs Larsen, F. Reibke Poulsen, A. Nørlund Christensen, S. E. Rasmussen, Acta Chem. Scand. 1970, 24, 1662-1670. The structural motif of four cyclically connected octahedra is also present in akaganéite, β-FeO(OH): P. Keller, Neues Jahrb. Miner. Ahh. 1970, 113, 29-49.
13. W.H. Baur, Mater. Res. Bull. 1981, 16, 339-345.
14. rutile in the CS terminology.
15. J. Burger, M. Kelemen, B. Pilawa, unpublished results: The magnetic susceptibility of several samples of 1 (m = 5-6 mg) have been determined with a SQUID magnetometer (Quantum Design: Magnetic Property Measurement System; magnetic field strengths from 0.1 to 20 kOe). The field dependence of the magnetization (room temperature) did not indicate ferromagnetic impurities in the samples.
16. III centers.
17. Cf. D. E. Kurtz, Chem. Rev. 1990, 90, 585-606.
18. J. E. Greedan, Encyclopedia of Inorganic Chemistry, Vol. 4 (Ed.: R. B. King), Wiley, New York, 1994, pp. 2017-2048.
19. J. B. Goodenough, Magnetism and the Chemical Bond, Wiley, New York, 1963, p. 136 and 240.
20. Three-dimensional linked patterns do not require an oxo ligand hapticity > 3, as stated in ref. [1].
21. S. L. Heath, J. M. Charnock, C. D. Garner, A. K. Powell, Chem. Eur. J. 1996, 2, 634-639, and references therein.
22. K. Hegetschweiler, L. Hausherr-Primo, W. H. Koppenol, V. Gramlich, L. Odier, W. Meyer, H. Winkler, A. X. Trautwein, Angew. Chem. 1995, 107, 2421-2423; Angew. Chem. Int. Ed. Engl. 1995, 34, 2242-2243.
23. K. Hegetschweiler, L. Hausherr-Primo, W. H. Koppenol, V. Gramlich, L. Odier, W. Meyer, H. Winkler, A. X. Trautwein, Angew. Chem. 1995, 107, 2421-2423; Angew. Chem. Int. Ed. Engl. 1995, 34, 2242-2243.
24. See for example: S. J. Lippard, J. M. Berg. Bioanorganische Chemie, Spektrum Akademischer Verlag, Heidelberg 1994, p. 140.