Synthesis Of Titanocene And Zirconocene Complexes Bearing Pendant Thieny/Phenyl-substituted Indenyl Ligand

Five new complexes containing hemilabile ligand were designed and synthesized, including three series as follows:(Ⅰ) Titanium complexes bearing pendant thienyl substituted indenyl ligand. The synthetic route was as follows:the reaction of thienyl lithium with corresponding fulvene afforded the target ligand after hydrolysis and purification; the ligand was treated with butyl lithium and then reacted with TiCl4 in hexane to give the target titanium complex. Complex Cl was obtained after recrystallization from hexane, which was further characterized by 1H NMR, EA methods.(Ⅱ) Zirconocene complexes bearing pendant thienyl substituted indenyl ligand. The synthetic route was as follows:the lithium salts of indenyl ligands bearing pendant thienyl group were reacted with CpZrCl3-DME in THF respectively to give the target complexes C3, C5, C6 after recrystallization from toluene or toluene/hexane. All complexes were further characterized by 1H NMR, EA and/or HRMS.(Ⅲ) Zirconocene complexes bearing pendant phenyl substituted indenyl ligand. The synthetic route was as follows:the reaction of phenyl lithium reacted with corresponding fulvene afforded the target ligand after hydrolysis and purification; the obtained ligand was treated with butyl lithium and then reacted with CpZrCl-DME in THF to give the target complex. Complex C8 was obtained after recrystallization from toluene/hexane, which was characterized by 1H NMR, EA or HRMS.