以吡啶鉗型配位基合成多功能之鈦錯合物及其應用探討

藉由 Ti(OiPr)4 和配位基 [ L1-4-H2] 在 25 or 40 °C於 THF溶液中反應生成 (L1-3) Ti(OiPr)2、[(L1)Ti]4 和 (L1)2 Ti。由X-ray單晶繞射可知 (L1) Ti(OiPr)2 和 (L2) Ti(OiPr)2 錯合物是五配位雙三角錐。[(L1)Ti]4是有四個鈦原子中間由氧橋接組成方型的錯合物。然而鈦金屬錯合物是可多功能運用，例如開環聚合反應、碳-磷耦合及生物活性測試。首先 ε - caprolactone 和 L - lactide 的開環聚合反應探討，可知鈦金屬錯合物立體障礙與推電子基之影響。此外，(L1-3) Ti(OiPr)2 錯合物對 rac-lactide 進行開環聚合，其 Pm 值是 0.64 到 0.65 間。使用 L1-H2、 (L1)Ti(OiPr)2、 [(L1)Ti]4 和 (L1)2Ti 進行生物毒殺人類乳癌細胞 (MDA-MB-231) 測試，由結果可知 [(L1)Ti]4 錯合物比其他鈦金屬錯合物和配位基 L1-H2 毒殺乳癌細胞效果更佳。最後鈦金屬錯合物也運用於碳-磷耦合反應之探討。

關鍵字

鈦金屬錯合物；開環聚合反應；碳-磷耦合；生物活性測試；人類乳癌細胞 (MDA-MB-231)

並列摘要

The synthesis, structural characterization, and reactivity of titanium complexes supported by tridentate pyridinyl alkoxides ligands are study. Alcoholysis of Ti(OiPr)4 with Ligands [ L1-4-H2] in THF at 25 or 40 °C generated (L1-3)Ti(OiPr)2, [(L1)Ti]4 and (L1)2Ti. Form the X-ray studies, (L1)Ti(OiPr)2 and (L2)Ti(OiPr)2 are five-coordinate, trigonal-bipyramidal species. [(L1)Ti]4 is a square tetranucleus, and titanium atoms bridge by four oxgens. However, titanium complexes are useful in multiple applications such as ring-opening polymerization, hydrophosphonylation and cytotoxic assay. The study of ring-opening polymerization (ROP) of ε - caprolactone and L - lactide revealed the Ti complexes with less steric bulky and electron-donating groups. In addition, the selectivity of rac-lactide ROP by (L1-3) Ti(OiPr)2 showed the isotactic PLA with Pm during 0.64 to 0.65. Using L1-H2, (L1)Ti(OiPr)2, [(L1)Ti]4 and (L1)2Ti assay with THF and their cytotoxicity toward human breast cancer cells (MDA-MB-231) was measured. The results showed [(L1)Ti]4 has the greatest cytotoxic activity for MDA-MB-231 compared with other titanium complexes and L1-H2. Finally, all the titanium complexes are catalytic active for the hydrophosphonylation.