Krempner C, Köckerling M, Reinke H, Weichert K
Institut für Chemie der Universität Rostock, A.-Einstein-Strasse 3a, D-18059 Rostock, Germany.
Inorg Chem. 2006 Apr 17;45(8):3203-11. doi: 10.1021/ic0514997.
The syntheses and structures of zirconium and titanium complexes containing the novel chelating trisilane-1,3-diolate ligand [Me2Si(R2SiO)2]2- (R = SiMe3) (5)-H2 are reported. The chloride complexes [Me2Si(R2SiO)2]TiCl2 (7a) and [Me2Si(R2SiO)2]ZrCl2 x 2 THF (7b) were prepared by the reaction of MCl4 (M = Ti, Zr) with [Me2Si(R2SiO)2]2Ti (6a) and [Me2Si(R2SiO)2]2Zr (6b), which are derived from the reaction of 5 with M(NEt2)4, respectively. In the presence of TiCl4, complexes 6a and 7a undergo a ring-opening reaction to produce the dinuclear complex [Me2Si(R2SiO)2][TiCl3]2 (9). [Me2Si(R2SiO)2]TiMe2 (10) and [Me2Si(R2SiO)2]TiBnz2 (11) were prepared in moderate yields from reactions of 7a with 2 equiv of MeMgBr and BnzMgCl, respectively. According to NMR spectroscopic investigations, the reaction of the dimethyltitanium complex 10 with B(C6F5)3 led to full exchange of both methyl groups by C6F5 groups under quantitative formation of [Me2Si(R2SiO)2]Ti(C6F5)2 (12) and a mixture of B(C6F5)(3-n)Me(n), where n = 1-3. The structure of 12 is further evidenced by the preparation of an identical sample from the reaction of 7a with 2 equiv of C6F5MgBr. Refluxing an ether solution of 12 surprisingly gave [Me2Si(R2SiO)2]2TiC6F5]2O (13) as a result of ether cleavage. The structures of the complexes 7a, 7b, 9, 10, and 13 were determined by X-ray crystallography, and structural discussion of the bond parameters will be given.
报道了含新型螯合三硅烷 - 1,3 - 二醇盐配体[Me2Si(R2SiO)2]2-（R = SiMe3）（5）-H2的锆和钛配合物的合成及结构。氯化物配合物[Me2Si(R2SiO)2]TiCl2（7a）和[Me2Si(R2SiO)2]ZrCl2·2THF（7b）分别通过MCl4（M = Ti，Zr）与[Me2Si(R2SiO)2]2Ti（6a）和[Me2Si(R2SiO)2]2Zr（6b）反应制备，而6a和6b分别由5与M(NEt2)4反应得到。在TiCl4存在下，配合物6a和7a发生开环反应生成双核配合物[Me2Si(R2SiO)2][TiCl3]2（9）。[Me2Si(R2SiO)2]TiMe2（10）和[Me2Si(R2SiO)2]TiBnz2（11）分别由7a与2当量的MeMgBr和BnzMgCl反应，以中等产率制备。根据核磁共振光谱研究，二甲基钛配合物10与B(C6F5)3反应导致两个甲基完全被C6F5基团取代，定量生成[Me2Si(R2SiO)2]Ti(C6F5)2（12）以及B(C6F5)(3 - n)Me(n)的混合物，其中n = 1 - 3。7a与2当量的C6F5MgBr反应制备相同样品进一步证明了12的结构。令人惊讶的是，12的醚溶液回流后由于醚键断裂生成了[Me2Si(R2SiO)2]2TiC6F5]2O（13）。通过X射线晶体学确定了配合物7a、7b、9、10和13的结构，并将给出键参数的结构讨论。
