Synthesis and Structures of Titanium and Zirconium Trisiloxides

The synthesis and structures of zirconium and titanium trisiloxides containing the tridentate ligand [MeSi(RMeSiO)3]3- (rac-l,l-3)-3H (R = Si(SiMe3)2Me) are reported. Reactions of rac-l,l-3 with M(OEt)4, where M = Ti or Zr, gave tridentate complexes of formula [MeSi(RMeSiO)3]MOEt (l,l-4, M = Ti; l,l-5, M = Zr). In striking contrast, treatment of rac-l,l-3 with Zr(NEt)4 afforded the spirocyclic complex {[MeSi(RMeSiO)3]2Zr}H2 (l,l-7). These compounds feature bicyclooctane structures, which are hitherto unknown in the chemistry of metal siloxides.

本文报道了含三齿配体[MeSi(RMeSiO)₃]³⁻（rac-l,l-3）-3H（R = Si(SiMe₃)₂Me）的锆与钛三硅氧烷化物的合成及结构表征。rac-l,l-3与M(OEt)₄（M为钛或锆）发生反应，得到通式为[MeSi(RMeSiO)₃]MOEt的三齿配合物（l,l-4，M=Ti；l,l-5，M=Zr）。与之形成鲜明对比的是，rac-l,l-3与Zr(NEt)₄反应则生成了螺环配合物{[MeSi(RMeSiO)₃]₂Zr}H₂（l,l-7）。上述化合物均具有双环辛烷结构，这在金属硅氧烷化学领域中迄今尚未见报道。