Zulys, A: Bidentate Amide Ligands in Rare Earth, Zinc

Various active non-cyclopentadienyl metal catalysts for organic transformation such as inter-, intramolecular hydroamination, hydosilylation and Tishchenko reaction are presented. This thesis describe the catalysis of bis(phosphinimino)methanide (BIPM) rare earth metal amide, cyclooctatetraenide (COT) and Iodide complexes as well as aminotroponiminate zinc amide, alkyl complexes as well as 1,2-bis((2,6-diisopropylphenyl)imino)acenaphthene (dpp-bian) magnesium complexes, and bis (alkylphenyl)formamido lanthanum complexes. The compounds used for these organic transformations were shown below. Hydroamination of alkynes and unactivated alkenes using Zn complexes was done for the first time in homogeneous catalysis. More sterically demanding spectator ligands enhanced the reaction rate of Zn complexes as follows (BIPM)ZnMe > (BDI)ZnMe > (ipr2ATI)ZnMe, as well as more labile leaving group ligands increased the reactivity of the catalyst where Alkyl > Amido. The enantiopure S,S-Zn2(ipr-ATIPh)2(Me2) X and S,S-Zn2(ipr-ATIPh)2(Et2) XI were investigated for enantioselective hydroamination of aminoalkenes. Unfortunately both complexes could not compete with other catalysts because of their lower activity and catalyzed only at elevated temperature. Bis(phosphin¬imino)methanide (BIPM) rare earth metal complexes were applied in the catalytic hydroamination of aminoalkyne and -alkenes. Altering the leaving group ligands of the complexes from stabile to labile ligand (cyclooctatetraenide and bisdimethylsilylamide) showed considerable change in activity of catalysts. Lanthanide complexes bearing more labile ligand (BDSA) XV exhibit good catalytic activities either for hydroamination, hydrosilylation and sequential hydroamination/hydrosilylation. BIPM halide lanthanide complexes showed good activity at elevated temperature (120 C), whereas BIPM cyclooctatetraenide lanthanide complexes, which have no leaving group showed only low activity at high temperature 120 C. The