Collect. Czech. Chem. Commun. 2000, 65, 1248-1261

Crystal Structures of Unusual Titanocene By-products from Attempted Dimerization of Terminal Alkynes

Róbert Gyepesa, Ivana Císařováa, Michal Horáčekb, Jiří Čejkab, Lidmila Petrusováb and Karel Machb,*

a Department of Inorganic Chemistry, Faculty of Science, Charles University, Hlavova 2030, 128 40 Prague 2, Czech Republic
b J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Dolejškova 3, 182 23 Prague 8, Czech Republic


Structures of unusual organometallic products μ-[(1,2,3,3a,7a-η):(3a,4,5,6,7,7a-η)-4,7- bis(trimethylsilyl)indenyl]-di-μ-hydridobis(η5-cyclopentadienyl)titanium(TiIII/TiII) (9) and μ-[(3,4,5-η):(4,5,6-η)-(E,E)-2,2,7,7-tetramethylocta-3,5-diene}bis{bis(η5-methylcyclopentadienyl)titanium} (10a) were determined by X-ray diffraction analysis. Compounds 9 and 10a arose as by-products in very low yields in the Ti(C5H5)22-Me3SiC≡CSiMe3)-HC≡CSiMe3 and Ti(C5H4Me)22-Me3SiC≡CSiMe3)-HC≡CCMe3 systems, respectively, when exposed to sunlight. Mechanisms of their formation were tentatively discussed.

Keywords: Titanium; Titanocenes; Metallocenes; Alkynes; Oligomerization; Indenyl bridge; Hydride bridge; Butadiene bridge; X-Ray diffraction.

References: 37 live references.