PhD ceremony: Shaozhong Ge, 11.00 uur, Academiegebouw, Broerstraat 5, Groningen
Thesis: Reactivity of rare erath metal organometallics.
Bearing ancillary ligand derived from the 1.4-diazepan-6-amine framework
Promotor(s): prof. B. Hessen
Faculty: Mathematics and Natural Sciences
Shaozhong Ge has shown that the 1,4-diazepan-6-amine moiety is suitable as a ligand framework for neutral and cationic organo rare earth metal chemistry. When the work described in the thesis of Ge started, the organometallic chemistry of rare earth metals was still in its infancy compared to that of transition metals. The aim of his thesis was to explore the reactivity and catalytic properties of welldefined neutral and cationic rare earth organometallics with an ancillary ligand system that allows for systematic variations. For this purpose, he has developed a series of neutral and monoanionic chelating ancillary ligands based on the 1,4,6-trimethyl-1,4-diazepan-6-amine (Me3DAPA) moiety and prepared a range of welldefined neutral and cationic rare earth metal alkyl and benzyl complexes supported by these ligands. These synthesized organometallic complexes catalyzes ethylene polymerization, intramolecular hydroamination/cyclization of aminoolefins, linear dimerization of terminal alkynes, and hydrosilylation of terminal alkenes. For linear dimerization of terminal alkynes, he proposed a new reaction mechanism to explain the observed Z-selectivity based on the stoichiometric reactions between catalyst precursors and substrates, the reactivity of isolated products from the stoichiometric reactions, and the kinetic investigations.
