This work provides original insights to the better understanding of the complex structure–activity relationship of ZrIV–pyridylamido-based olefin polymerization catalysts and highlights the importance of the metal-precursor choice (ZrACHTUNGTRENUNG(NMe2)4 vs. Zr(Bn)4) to prepare precatalysts of unambiguous identity. A temperature-controlled and reversible s-bond metathesis/protonolysis reaction is found to take place on the ZrIV-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 bisamido–mono-amino complexes featured by tridentate dianionic {N,N,C} ligands).
Facing Unexpected Reactivity Paths with ZrIV-Amidopyridinate Polymerization Catalyst / L. Luconi;A. Rossin;G. Tuci;I. Tritto;L. Boggioni;J. J. Klosin;C. N. Theriault;G. Giambastiani. - In: CHEMISTRY-A EUROPEAN JOURNAL. - ISSN 0947-6539. - ELETTRONICO. - 18:(2012), pp. 671-687. [10.1002/chem.201102194]
Facing Unexpected Reactivity Paths with ZrIV-Amidopyridinate Polymerization Catalyst
LUCONI, LAPOMembro del Collaboration Group
;GIAMBASTIANI, GIULIANO
2012
Abstract
This work provides original insights to the better understanding of the complex structure–activity relationship of ZrIV–pyridylamido-based olefin polymerization catalysts and highlights the importance of the metal-precursor choice (ZrACHTUNGTRENUNG(NMe2)4 vs. Zr(Bn)4) to prepare precatalysts of unambiguous identity. A temperature-controlled and reversible s-bond metathesis/protonolysis reaction is found to take place on the ZrIV-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 bisamido–mono-amino complexes featured by tridentate dianionic {N,N,C} ligands).File | Dimensione | Formato | |
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