P-N-Liganden in der Lanthanoid-, Zirkonium- und (English shop)

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Since the beginning of the 1980s, the field of lanthanide chemistry has increasingly attracted research interest owing to the interesting chemical properties of the “rare earths”. To date, cyclopentadienyl derivatives have mainly been employed as ligand systems. More recently, research interest has focused on the investigation of alternative ligands such as amides or alkoxides. This approach was realised in the present work using the P–N ligand systems bis(phosphinimino)methane and bis(t-butylamido)cyclodiphosph(III)azane. The bis(phosphinimino)methane complexes obtained were investigated with regard to their catalytic activity in intramolecular hydroamination and intermolecular hydrosilylation. In addition, the application of lanthanide catalysts for sequential hydroamination / cyclisation is described for the first time. The bis(t-butylamido)cyclodiphosph(III)azane ligands were furthermore used in aluminium alkyl chemistry. Unexpected Lewis acid/base adducts could be isolated and characterised. The last part of the work reports on the use of chiral P–N ligands in zirconocene chemistry.

Keywords:
lanthanides, yttrium, lanthanum, rare earths, amides, P–N ligands, cyclodiphosph(III)azane, intramolecular hydroamination, intermolecular hydrosilylation, sequential hydroamination / hydrosilylation, aluminium alkyls, organometallic chemistry.