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] (Journal article)

Stamatatos, T. C./ Perlepes, S. P./ Manos, M. J./ Tasiopoulos, A. J./ Klouras, N.

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.
Institution and School/Department of submitter: Πανεπιστήμιο Ιωαννίνων. Σχολή Θετικών Επιστημών. Τμήμα Χημείας
Keywords: tris(cyclopentadienyl)hexamethoxido-oxidotrititanium(iv) triiodide,bis(eta(5)-cyclopentadienyl)diiodotitanium(iv),triangular titanium(iv) complexes,methanolysis route,crystal structures,reactivity studies,crystal-structure,titanocene dichloride,titanium(iv) complexes,solid-state,trinuclear,chemistry,spectra,halides,polymerization,zirconocene
URI: http://olympias.lib.uoi.gr/jspui/handle/123456789/9806
ISSN: 0095-8972
Link: <Go to ISI>://000299441700017
Publisher: Elsevier
Appears in Collections:Άρθρα σε επιστημονικά περιοδικά ( Ανοικτά)

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