Neutral ZrIV and HfIV dimethyl complexes stabilized by unsymmetrical dianionic {N,C,N’} pincer ligands have been prepared from their corresponding bis-amido complexes upon treatment with AlMe3. Their structure consists of a centralσ-bonded aryl donor group (C) capable of forming robust M–C bonds with the metal center, enforced by the synergic effect of both the coordination of peripheral donor groups (N) and the chelating rigid structure of the {N,C,N} ligand framework. Such a combination translates into systems having a unique balance between stability and reactivity. These ZrIV and HfIV dimethyl complexes were convertedin situ into cationic species [MIV{N−,C−,N}Me][B(C6F5)4] which are active catalysts for the room temperature (r.t.) intramolecular hydroamination/cyclization of primary and secondary aminoalkenes as well as for the high temperature ethylene–1-octene copolymerizations.

Cationic Group-IV pincer-type complexes for polymerization and hydroamination catalysis / Lapo Luconi;Jerzy Klosin;Austin J. Smith;Stéphane Germain;Emmanuelle Schulz;Jérôme Hannedouche;Giuliano Giambastiani. - In: DALTON TRANSACTIONS. - ISSN 1477-9226. - STAMPA. - 42:(2013), pp. 16056-16065. [10.1039/c3dt51620b]

Cationic Group-IV pincer-type complexes for polymerization and hydroamination catalysis

LUCONI, LAPO;GIAMBASTIANI, GIULIANO
2013

Abstract

Neutral ZrIV and HfIV dimethyl complexes stabilized by unsymmetrical dianionic {N,C,N’} pincer ligands have been prepared from their corresponding bis-amido complexes upon treatment with AlMe3. Their structure consists of a centralσ-bonded aryl donor group (C) capable of forming robust M–C bonds with the metal center, enforced by the synergic effect of both the coordination of peripheral donor groups (N) and the chelating rigid structure of the {N,C,N} ligand framework. Such a combination translates into systems having a unique balance between stability and reactivity. These ZrIV and HfIV dimethyl complexes were convertedin situ into cationic species [MIV{N−,C−,N}Me][B(C6F5)4] which are active catalysts for the room temperature (r.t.) intramolecular hydroamination/cyclization of primary and secondary aminoalkenes as well as for the high temperature ethylene–1-octene copolymerizations.
2013
42
16056
16065
Lapo Luconi;Jerzy Klosin;Austin J. Smith;Stéphane Germain;Emmanuelle Schulz;Jérôme Hannedouche;Giuliano Giambastiani...espandi
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Utilizza questo identificatore per citare o creare un link a questa risorsa: https://hdl.handle.net/2158/823559
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