Cationic Group-IV pincer-type complexes for polymerization and hydroamination catalysis.
Neutral Zr(IV) and Hf(IV) 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 central σ-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 Zr(IV) and Hf(IV) dimethyl complexes were converted in situ into cationic species [M(IV){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.
Institute of Chemistry of OrganoMetallic Compounds ICCOM-CNR, Via Madonna del Piano, 10-50019, Sesto F.no., Florence, Italy. giuliano.giambastiani@iccom.cnr.it.
Lapo
L
Luconi
Jerzy
J
Klosin
Austin J
AJ
Smith
Stéphane
S
Germain
Emmanuelle
E
Schulz
Jérôme
J
Hannedouche
Giuliano
G
Giambastiani