C. Lee, Young-Hye La, Soojin Park
Jul 21, 1998
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0
Influential Citations
43
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Journal
Organometallics
Abstract
The reaction of 1,8-diaminonaphthalene with trimethylchlorosilane and tri(isopropyl)chlorosilane gives N,N‘-disilylated products (1a,b) in moderate yields. Double deprotonation of 1a,b with n-BuLi yields the dilithiated products (2a,b) in 78−85% yield. The reaction of 2a,b with TiCl4 produces diamidotitanium(IV) dichlorides, {1,8-C10H6(NSiMe3)2}TiCl2 (3a) and {1,8-C10H6(NSi(i-Pr)3)2}TiCl2 (3b). The crystal structure of 3a shows that the complex has an unusually large Cl−Ti−Cl angle (120.5°). Meanwhile, the bulkier substituents on the nitrogen atoms of 3b are significantly away from the naphthalene plane. The reaction of 2a,b with ZrCl4 produces a bis(diamido)zirconium(IV) complex {1,8-C10H6(NSiMe3)2}2Zr (4a) and a diamidozirconium(IV) dichloride {1,8-C10H6(NSi(i-Pr)3)2}ZrCl2 (4b), respectively. The crystal structure of 4b shows that the molecule forms a dimer associated through two chloro bridges in the solid state. Facile monomethylation and transmetalation of 3a to form a dinuclear aluminum complex (5) ...