NOVEL FERRICENIUM POLYIODIDES. Karl-Friedrich Tebbe, Rita Buchem, Institut für Anorganische Chemie der Universität zu Köln, D-50939 Köln, Greinstraße 6, Germany

Probable ferricenium polyiodides FcI_n (n > 1) except for a triiodide FcI₃ [1 ] are only poorly characterized [2]. During systematic investigations of polyiodide series with suitable cations we proved the compounds of this type with n = 4.33, 5, 7, 8, 9.67 [3] from which the crystal structures of the ferricenium heptaiodide FcI₇, [4], the bisferricenium hexadecaiodide (Fc)₂I₁₆ [5] and a trisferricenium nonacosaiodide (Fc)₃I₂₉ [6] have been solved. Particularly the latter is worth mentioning (FcI_9.67, P2₁/m, Z = 6, a = 10.631 Å, b =- 18.163 Å, c = 20.377 Å, [[beta]] = 91.31deg., R = 0.059), as it is the polyiodide with the largest iodine excess so far [7] containing also hitherto scarcely observed formally three times charged polyiodide ions [8]. Similar reactions of the substituted complexes 1,1'-dimethylferrocene and decamethylferrocene with iodine produce diMeFcI_n with n = 3 [9], 5, 7 and decaMeFcI_n with n = 3, 5, 6.5 [10]. These frequently in the anionic iodine part highly connected crystal structures will be presented, described, compared and explained.

[ 1] Bernstein, T. & Herbstein, F. H. (1968). Acta Cryst. B24, 1640.

[ 2] Neuse, E. W. & Loonat, M. S. (1985). J. Organomet. Chem. 286, 329.

[ 3] Tebbe, K.-F. & Buchem, R. (1995). Z. Kristallogr Suppl. Issue 9, 353.

[ 4] Tebbe, K.-F. & Buchem, R. (1995). Z. Kristallogr. 21O, 438.

[ 5] Tebbe, K.-F. & Buchem, R. (1996). Z. Kristallogr., in print.

[ 6] Tebbe, K.-F. & Buchem, R. (1996). Angew. Chem., to be submitted.

[ 7] Tebbe, K.-F. (1988). Z. Kristallogr. 185, 496; Tebbe, K.-F., Lindenthal, W. & Farida, T. (1991). Z. Kristallogr. Suppl. Issue 4, 203.

[ 8] Tebbe, K.-F. (1996). Z. Kristallogr. Suppl. Issue, in print.

[ 9] Bats, J. W., de Boer, J. J. & Bright, D. (1971). Inorg. Chim. Acta 5, 605.

[10] Tebbe, K.-F. & Buchem, R., papers in preparation.