Cyclopentadienylphosphazen-Constrained-Geometry-Komplexe der 4. Gruppe und ausgewählter Hauptgruppenelemente

Constrained geometry complexes (CGCs) of the forth group based upon the cyclopentadienyl-silylamido (CpSiN) ligand belong to one of the best developed classes of chelating cyclopentadienyl-amido early transition metal complexes. They have found industrial application as single site olefin polymerization catalysts. In order to improve or modify the catalytic properties ligand modifications have played an in the development of new single site group 4 catalyst precursors. The present work deals with the synthesis of complexes with monoanionic, bifunctional cyclopentadienyl-phosphazenes ligands (CpPN), a new class of constrained geometry ligands in which a phosphazene unit displaces the silylamido moiety. Tetravalent cationic complexes on the basis of the cyclopentadienyl-phosphazenes ligands (CpPN) are isoelectronic to group 4 transition metal complexes of type CpSiN ligand. Chapter 1 is dedicated to the synthesis and characterization of the CpPN ligands, their alkaline derivatives and cyclopentadienyl-phosphane precursors. In chapter 2 (zirconium), 3 (titanium) and 4 (hafnium) synthethic routes to CpPN complexes of the forth group are presented. Chapter 5 (aluminium) and 6 (magnesium) deal with the preparation of respective main group derivatives. The preparation of titanium complexes with the related dianionic cyclopentadienyl-phosphoraniminato ligand [C5R4PR2N]2- is discussed in chapter 7. In Chapter 8 a new synthetic methodology for the preparation of CpPN ligands is introduced by an „anionic type“ of the STAUDINGER reaction. In addition with the linked cyclopentadienyl-phosphazido ligands a new type of CG ligand an their coordination to alkalines and zirconium is presented. At last the chapters 9 and 10 deal with the application of the prepared functional molecules in polymerization and hydroamination catalysis.