Unexpected formation, X-ray structure, and characterization of the triangular [Ti3O(OMe)6(σ5-C 5H5)3](I3) complex from hydrolysis and methanolysis of [Ti(σ5-C5H5) 2I2]
ΣυγγραφέαςStamatatos, Theocharis C.
Perlepes, Spyros P.
Manos, Manolis J.
Tasiopoulos, Anastasios J.
SourceJournal of Coordination Chemistry
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MetadataΕμφάνιση πλήρους εγγραφής
A convenient route has been developed for the formation of [Ti IV3O(OMe)6(σ5-C 5H5)3](I3) (2) involving methanolysis (and possibly hydrolysis) of species derived from titanocene diiodide, [TiIV(σ5-C5H5) 2I2] (1), under aerobic conditions. Single-crystal X-ray crystallography reveals that the cation of 2 consists of three TiIV's in a triangular arrangement bridged by a central 3-oxidethe latter lies 0.686A ° out of the Ti3 plane. Each edge of the triangle is bridged by oxygen of σ1 :μ-MeO. Terminal ligation is provided by three methoxide and three cyclopentadienyl groups. All TiIV 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 O 2, MeO, and σ5-C5Hσ5 . A proposal for the mechanism of the unexpected formation of the triiodide (I3) counteranion that is present in the crystal structure of 2 is also provided. © 2011 Taylor & Francis.