By P. C. Wailes
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Extra info for Organometallic Chemistry of Titanium, Zirconium, and Hafnium
Sample text
Russian workers (D41, N28, N37, N41) have measured the infrared spectra in the region 400-4000 cm " 1 for a number of mono(cyclopentadienyl)titanium derivatives including halides and alkoxides and have used the data to study the nature of the T i - C p bond as a function of the ligands connected to the central atom. According to Fritz (F27), the infrared bands assigned to vibrations of the cyclopentadienyl ligands shift toward longer wavelengths with an increase in the ionic character of the metal-Cp bond.
The alkoxides and phenoxides of C p T i I V are generally colorless to yellow. Those which have been tested appear to be sensitive to water and alcohols. With HC1 they form C p T i C l 3. Hydrolysis generally results in rupture of the T i - C p bond as well as the alkoxide bonds. F r o m the rate of alcoholysis of a group of cyclopentadienyltitanium trisphenoxides, it was found that the nature of the substituents on the phenoxide exerts a notice able influence on the character of the T i - C p bond (N40).
The metal-carbon stretching frequencies are at 540 and 505 c m - 1. F. TETRAALKYL- AND TETRAARYLTITANIUM COMPOUNDS 5. 1]hept-l-yltitanium [ Tetra (1-norbornyl) titanium] This yellow, diamagnetic compound was prepared in 9 0 % yield from T i C l 4- 2 T H F and the lithium alkyl (B60). At 100°, it has a half-life of 29 hr. In isoctane solution it is stable in the air. It does not form adducts with pyri dine, presumably for steric reasons. 6. Tetra (silylmethyI) titanium Compounds Lappert et al. (C41a) have recently reported the preparation of compounds of the type ( R 2R ' S i C H 2) 4T i (in which R = R' = C H 3 ; R = C 6 H 5 , R' = C H 3 ; R = C H 3 , R' = C 6 H 5 or C 6 H 5 C H 2 ) .