Crystal-chemical analysis of 312 compounds containing complexes [Ru a X b ] z– (X = O, S, Se, Te) is performed using Voronoi–Dirichlet polyhedra (VDP) and the method of intersecting spheres. In most of these complexes, Ru atoms have coordination number (CN) 6 and form RuX6 octahedra. However, only with respect to oxygen do the Ru(V)–Ru(VII) atoms exhibit CN 5 or 4 with trigonal-bipyramidal and tetrahedral coordination, respectively.The effect of the valence state of the Ru atoms on their stereochemistry is considered. The important role of the Ru–Ru interactions in the structure of the Ru(II)–Ru(V) compounds is established. As a result of the Ru–Ru interactions, the RuX6 octahedra are linked through a face or common edge or give O5Ru–RuO- dimers in which every metal atom occupies one of the vertices of an octahedron formed by the neighboring Ru atom.The dependence of the Ru–Ru and Ru–O bond orders on their lengths is established on the basis of a crystal-structure analysis and the 18-electron rule.
Russian Journal of Coordination Chemistry – Springer Journals
Published: Oct 13, 2004
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