Reactivity of rare earth metal organometallics bearing ancillary ligands derived the 1,4-Diazepan-6-amine framework

When the work described in this thesis started, the organometallic chemistry of rare earth metals was still in its infancy compared to that of transition metals. The aim of this thesis was to explore the reactivity and catalytic properties of well-defined neutral and cationic rare earth organometallics with an ancillary ligand system that allows for systematic variations. For this purpose, we have 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 well-defined 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, we 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.
Additionally, we describe the use of another type of ligand, the sterically demanding guanidinate [Me2NC(NAr)2]- (Ar = 2,6-iPr2C6H3), for synthesis of scandium, yttrium, and lanthanum alkyl complexes. By performing the comparative study of yttrium guanidinate complex and its amidinate analogues [RNC(NAr)2]Y(CH2SiMe3)2(THF) (R = Ph, Me-p-Ph, and C6F5; Ar = 2,6-iPr2C6H3) in the catalytic hydroamination/cyclization reaction of aminoolefins and the hydrosilylation reaction of terminal alkenes, we show that both the steric and electronic properties of the ancillary ligands have a significant influence on catalytic performances of this family of catalysts.

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