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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 26, Number 2
BKCSDE 26(2)
February 20, 2005 

Syntheses and Structures of 1,2,3-Substituted Cyclopentadienyl Titanium(IV) Complexes
Dae June Joe, Bun Yeoul Lee*, Dong Mok Shin
Cyclopentadienyl, Titanium, X-ray structure
Cyclopentadiene compounds, 2-[CR'R(OMe)]-1,3-Me2C5H3 (R, R' = 2,2'-biphenyl, 2) and 2-[CR'R(OSiMe3)]- 1,3-Me2C5H3 (R, R' = 2,2'-biphenyl, 3; R = ph, R' = ph, 4; R = 2-naphthyl, R' = H, 5) are readily synthesized from 2-bromo-3-methoxy-1,3-dimethylcyclopentene (1). Reaction of the cyclopentadienes with Ti(NMe2)4 in toluene results in clean formation of the cyclopentadienyl tris(dimethylamido)titanium complexes, which are transformed to the trichloride complexes, 2-[CR'R(OMe)]-1,3-Me2C5H2}TiCl3 (R, R' = 2,2'-biphenyl, 6) and {2-[CR'R(OSiMe3)]-1,3-Me2C5H2}TiCl3 (R, R' = 2,2'-biphenyl, 7; R = ph, R' = ph, 8; R = 2-naphthyl, R' = H, 9). Attempts to form C1-bridged Cp/oxido complexes by elimination of MeCl or Me3SiCl were not successful. X-ray structures of 6, 7 and an intermediate complex {2-[Ph2C(OSiMe3)]-1,3-Me2C5H2}TiCl2(NMe2) (10) were determined.
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