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- W2106390799 abstract "Abstract This work provides original insights to the better understanding of the complex structure–activity relationship of Zr IV –pyridylamido‐based olefin polymerization catalysts and highlights the importance of the metal‐precursor choice (Zr(NMe 2 ) 4 vs. Zr(Bn) 4 ) to prepare precatalysts of unambiguous identity. A temperature‐controlled and reversible σ‐bond metathesis/protonolysis reaction is found to take place on the Zr IV ‐amido complexes in the 298–383 K temperature range, changing the metal coordination sphere dramatically (from a five‐coordinated tris‐amido species stabilized by bidentate monoanionic {N,N − } ligands to a six‐coordinated bis‐amido–mono‐amino complexes featured by tridentate dianionic {N − ,N,C − } ligands). Well‐defined neutral Zr IV –pyridylamido complexes have been prepared from Zr(Bn) 4 as metal source. Their cationic derivatives [Zr IV {N − ,N,C − }Bn] + [B(C 6 F 5 ) 4 ] − have been successfully applied to the room‐temperature polymerization of 1‐hexene with productivities up to one order of magnitude higher than those reported for the related Hf IV state‐of‐the‐art systems. Most importantly, a linear increase of the poly(1‐hexene) M n values (30–250 kg mol −1 ) has been observed upon catalyst aging. According to that, the major active species (responsible for the increased M n polymer values) in the aged catalyst solution, has been identified." @default.
- W2106390799 created "2016-06-24" @default.
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- W2106390799 date "2011-12-06" @default.
- W2106390799 modified "2023-10-18" @default.
- W2106390799 title "Facing Unexpected Reactivity Paths with ZrIV-Pyridylamido Polymerization Catalysts" @default.
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- W2106390799 doi "https://doi.org/10.1002/chem.201102194" @default.
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