| Abstract |
The reactions of [Zr(NMe2)(4)](2) with triamido-triazacyclonane ligand precursors, \NH(Ph)SiMe2\(3)tacn (H3N3[9]N-3) and \NH(C6H4F)SiMe2\(3)tacn (H3N3-F[9]N-3), led to the formation of complexes [Zr(NMe2)(2)\N(Ph)SiMe2\(2)\NH(Ph) SiMe2\tacn], 1, and [Zr(NMe2)(2)\N(o-C6H4F)SiMe2\(2)\NH(o-C6H4F)SiMe2\ tacn], 2, where the zirconium is coordinated to two remaining dimethylamido ligands and to a dianionic tacn-based ligand, [\N(Ph )SiMe2\(2)\NH(Ph )SiMe2\tacn](2-), that formed from deprotonation of two amine pendent arms of the ligands precursors. The third pendent arm of H3N3[9]N-3 and H3N3-F[9]N-3 remains neutral and not bonded to the zirconium. Treatment of 1 with NaH led to the synthesis of [Zr(NMe2)\N(Ph)SiMe2\(2)tacn], 3, that results from the cleavage of the N-Si bond of the original neutral pendent arm. Complexes [ZrCl\N(Ph )SiMe2\(2)tacn] (Ph = C6H5, 4, and C6H4F, 5) have been obtained by reactions of ZrCl4 with \MN(Ph )SiMe2\(3)tacn center dot 2THF (M = Li, Na). Reactions of 4 and 5 with LiCCPh led to the syntheses of [Zr(CCPh)\N(Ph )SiMe2\(2)tacn] (Ph = C6H5, 6, and C6H4F, 7). The solid-state structure of 3 shows a chiral metal center. |
