Reactivity of C1 -Symmetric Heteroarylamido Hafnium Complexes towards Unsaturated Electrophilic Molecules: Development of New Families of Olefin Polymerization Catalysts.

Heteroarylamido hafnium post-metallocenes with [C,N,N] ligands were functionalized by the insertion of small electrophilic unsaturated molecules into the CAr -Hf bond of the ligand, which gave rise to various 1,1- and 1,2-insertion complexes with the modified ligands of previously unknown [O,N,N], [N,N,N], [O,N,N,N], and [N,N,N,N] types. It was found that C1 symmetry of the starting complexes, in some cases, results in the formation of two diastereoisomers after 1,1- or 1,2-insertion. Most of the obtained novel complexes were shown to form active catalysts for olefin polymerization in the presence of MAO (methylaluminoxane). Thus, a new approach to the feasible and easy "late stage" modification of the precatalyst structure has been suggested; it can be performed immediately prior to the polymerization tests without isolation and even in a high-throughput manner.

Reversible C-C bond formation in group 4 metal complexes: nitrile extrusion via ß-aryl elimination.

Pyridylamides of zirconium and hafnium with [C,N,N]-ligands reversibly insert nitriles into M-CAr bonds leading to an observable equilibrium between the starting [C,N,N]-complexes and newly formed [N,N,N]-complexes with a ketimide moiety in a 7-membered metallacycle. The discovered reversible insertion of nitriles into M-CAr bonds represents an unprecedented example of ß-aryl elimination from a ketimide ligand in early transition metal complexes. Experimental and computational studies suggest thermodynamic and electronic reasons for this reactivity. Weak orbital overlap between the ketimide nitrogen and the metal, and an unfavorable 7-membered metallacycle destabilize the product of insertion into the M-CAr bond, while the pyridylamide moiety acts as a directing group making the reverse process viable. The influence of non-chelate spectator ligands on the metal center and substituents in nitrile on the thermodynamic stability of the [N,N,N]-complexes was also studied. Exploiting ß-carbon elimination in complexes of early transition metals may extend the range of catalysts that are accessible for C-C activation processes in the future.

Multisubstituted C2-symmetric ansa-metallocenes bearing nitrogen heterocycles: influence of substituents on catalytic properties in propylene polymerization at higher temperatures.

In this work we systematically studied the effects of modifications of substituents on the performance of the isospecific zirconocene-based catalyst family, Me2Si(2-Alk-4-(N-carbazolyl)Ind)ZrX2 (X = Cl, Me), wherein the progenitor was shown to be particularly suitable in high-temperature propylene polymerization processes. In order to obtain the required zirconocenes, we developed a novel synthetic pathway to 4-(N-carbazolyl)indenes through Pd-catalyzed cyclizations of 2,2'-dibromobiaryls with 4-aminoindenes, which were synthesized via Buchwald-Hartwig reaction or electrophilic amination of 4-indenyl Grignard reagents with trimethylsilylmethyl azide. By a number of examples, the anion-promoted rac-to-meso isomerization method was shown to work reliably well for preparation of rac-ZrMe2-complexes. Certain zirconocenes among the 21 tested in propylene polymerization at 70 and 100 °C under MAO or borate activation outperformed the parent catalyst in molecular weight capability, regio- or stereoselectivity.

Pyridylamido hafnium complexes with a silylene bridge: synthesis and olefin polymerization.

The synthesis and characterisation of six novel Cs-symmetric pyridylamido hafnium complexes with a silylene bridge of the type [ArPy(R2Si)NAr']HfAlk2 are reported. Four complexes have been structurally characterised using single crystal X-ray diffraction. Appreciable differences between the solid state structures of these complexes and the pyridylamido hafnium complexes with a CRR' bridge were noted. Reactions with B(C6F5)3, [Ph3C][B(C6F5)4] and [HMe2NPh][B(C6F5)4] yielded active catalysts for the homopolymerisations of propene and 1-hexene and ethene/1-octene copolymerization. In spite of the Cs-symmetry of the precatalysts, isotactically enriched polypropylene and poly(1-hexene) were obtained. The fact that the mechanism of the catalyst activation includes the insertion of alkene into the Hf-CAr bond was demonstrated. It was found that the structures of Ar and the R2Si bridge influence the activity, molecular weight capability and 1-octene affinity of the catalysts.