Na6[Ge10{Fe(CO)4}8] ·18THF: A centaur polyhedron of germanium atoms

Angewandte Chemie - International Edition

Volumn 45, Issue 32, 2006, Pages 5373-5376

  Schnepf, Andreas ^a   Schenk, Christian ^a  

^a UNIVERSITY OF KARLSRUHE   (Germany)

Author keywords

Centaur polyhedron; Cluster compounds; Density functional calculations; Germanium

Indexed keywords

ATOMS; GERMANIUM COMPOUNDS; STRUCTURE (COMPOSITION);

CENTAUR POLYHEDRON; CLUSTER COMPOUNDS; DENSITY FUNCTIONAL CALCULATIONS;

SODIUM COMPOUNDS;

EID: 33747887029     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200600928     Document Type: Article

References (49)

1. A. Schnepf, Angew. Chem. 2004, 116, 682;
2. Angew. Chem. Int. Ed. 2004, 43, 664;
3. A. Schnepf, Coord. Chem. Rev. 2006, in press.
4. m] (n > m): A. Purath, R. Köppe, H. Schnöckel, Angew. Chem. 1999, 111, 3114;
5. Angew. Chem. Int. Ed. 1999, 38, 2926.
6. A. Sekiguchi, Y. Ishida, Y. Kabe, M. Ichinohe, J. Am. Chem. Soc. 2002, 124, 8776.
7. A. F. Richards, H. Hope, P. P. Power, Angew. Chem. 2003, 115, 4205;
8. Angew. Chem. Int. Ed. 2003, 42, 4071.
9. A. F. Richards, M. Brynda, M. M. Olmstead, P. P. Power, Organometallics 2004, 23, 2841.
10. A. Schnepf, Phosphorus Sulfur Silicon Relat. Elem. 2004, 179, 695.
11. A. Schnepf, R. Köppe, Angew. Chem. 2003, 115, 940;
12. Angew. Chem. Int. Ed. 2003 42, 911.
13. A. Schnepf, C. Drost, Dalton Trans. 2005, 3277.
14. A. Schnepf, Angew. Chem. 2003, 115, 2728;
15. Angew. Chem. Int. Ed. 2003, 42, 2624.
16. A. Schnepf, R. Köppe, Z. Anorg. Allg. Chem. 2002, 2914.
17. 3] + 4 NaBr. Therefore, the central germanium atom in 8 can be assigned a formal oxidation state of + 4, and thus every iron atom has the ideal value of 18 valence electrons.
18. Similar to the description of the centaur in Greek mythology (half human, half horse), a polyhedron built through the fusion of two different polyhedrons (here: half cube, half icosahedron) can be called a centaur polyhedron. C. Rocaniere, J. P. Laval, P. Dehaudt, B. Gaudreau, A. Chotard, E. Suard, J. Solid State Chem. 2004, 177, 1758.
19. [14] the synthetic method introduced by us might give access to such germanium subhalides.
20. 2-. C. Klemp, M. Bruns, J. Gauss, U. Häussermann, G. Stößer, L. van Wüllen, M. Jansen, H. Schnöckel, J. Am. Chem. Soc. 2001, 123, 9099;
21. C. Klemp, R. Köppe, E. Weckert, H. Schnöckel, Angew. Chem. 1999, 111, 1852;
22. Angew. Chem. Int. Ed. 1999, 38, 1740.
23. J. Campbell, G. J. Schrobilgen, Inorg. Chem. 1997, 36, 4078.
24. T. F. Fässler, U. Schütz, Inorg. Chem. 1999, 38, 1866.
25. C. H. E. Belin, J. D. Corbett, A. Cisar, J. Am. Chem. Soc. 1977, 99, 7163.
26. L. Xu, S. C. Sevov, J. Am. Chem. Soc. 1999, 121, 9245.
27. P. Kircher, G. Huttner, K. Heinze, G. Renner, Angew. Chem. 1998, 110, 1754;
28. Angew. Chem. Int. Ed. 1998, 37, 1756.
29. A great variety of transition-metal-substituted Zintl ions are known. However, in these cluster compounds the transition metal is part of the polyhedron and not a ligand. Thus, these compounds do not belong to the compounds described here. B. Kesanli, J. Fettinger, B. Eichhorn, Chem. Eur. J. 2001, 7, 5277;
30. B. Kesanli, J. Fettinger, D. R. Gardner, B. Eichhorn, J. Am. Chem. Soc. 2002, 124, 4779;
31. J. Campbell, H. P. A. Mercier, H. Franke, D. P. Santry, D. A. Dixon, G. J. Schrobilgen, Inorg. Chem. 2002, 41, 86;
32. L. Yong, S. D. Hoffmann, T. F. Fässler, Eur. J. Inorg. Chem. 2005, 3663.
33. J. D. Corbett, Angew. Chem. 2000, 112, 682;
34. Angew. Chem. Int. Ed. 2000, 39, 670;
35. T. F. Fässler, Angew. Chem. 2001, 113, 4289;
36. Angew. Chem. Int. Ed. 2001, 40, 4161;
37. T. F. Fässler, Coord. Chem. Rev. 2001, 215, 347.
38. K. Wade, Adv. Inorg. Chem. Radiochem. 1976, 18, 1.
39. Quantum-chemical calculations were carried out with the RI-DFT version of the TURBOMOLE program package by employing the Becke-Perdew86 functional. The basis sets were of SVP quality. The electronic structure was analyzed with the Ahlrichs-Heinzmann population analysis as based on occupation numbers. TURBOMOLE: O. Treutler, R. Ahlrichs, J. Chem. Phys. 1995, 102, 346;
40. BP86 functional: J. P. Perdew, Phys. Rev. B 1986, 33, 8822;
41. A. D. Becke, Phys. Rev. A 1988, 38, 3098;
42. RI-DFT: K. Eichkorn, O. Treutler, H. Öhm, M. Häser, R. Ahlrichs, Chem. Phys. Lett. 1995, 240, 283;
43. SVP: A. Schäfer, H. Horn, R. Ahlrichs, J. Chem. Phys. 1992, 97, 2571;
44. Ahlrichs-Heinzmann population analysis: E. R. Davidson, J. Chem. Phys. 1967, 46, 3320;
45. K. R. Roby, Mol. Phys. 1974, 27, 81;
46. R. Heinzmann, R. Ahlrichs, Theor. Chim. Acta 1976, 42, 33;
47. C. Erhardt, R. Ahlrichs, Theor. Chim. Acta 1985, 68, 231.
48. 2) is 1.04.
49. G. M. Sheldrick, SHELXTL, Version 5.1, Bruker AXS, 1998.