Unexpected formation, X-ray structure, and characterization of the triangular [Ti3O(OMe)(6)(eta(5)-C5H5)(3)](I-3) complex from hydrolysis and methanolysis of [Ti(eta(5)-C5H5)(2)I-2]
Unexpected formation, X-ray structure, and characterization of the triangular [Ti3O(OMe)(6)(eta(5)-C5H5)(3)](I-3) complex from hydrolysis and methanolysis of [Ti(eta(5)-C5H5)(2)I-2]
(EN)
Stamatatos, T. C.
(EN)
Πανεπιστήμιο Ιωαννίνων. Σχολή Θετικών Επιστημών. Τμήμα Χημείας
(EL)
Stamatatos, T. C.
(EN)
A convenient route has been developed for the formation of [(Ti3O)-O-IV(OMe)(6)(eta(5)-C5H5)(3)](I-3) (2) involving methanolysis (and possibly hydrolysis) of species derived from titanocene diiodide, [Ti-IV(eta(5)-C5H5)(2)I-2] (1), under aerobic conditions. Single-crystal X-ray crystallography reveals that the cation of 2 consists of three Ti-IV's in a triangular arrangement bridged by a central mu(3)-oxide; the latter lies 0.686 angstrom out of the Ti-3 plane. Each edge of the triangle is bridged by oxygen of eta(1) : mu-MeO-. Terminal ligation is provided by three methoxide and three cyclopentadienyl groups. All Ti-IV centers are five-coordinate in an extremely distorted geometry. IR and electronic data are discussed in terms of the known structure and coordination modes of O2-, MeO-, and eta(5)-C5H5-. A proposal for the mechanism of the unexpected formation of the triiodide (I-3(-)) counteranion that is present in the crystal structure of 2 is also provided.
(EN)
