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

被引:22
作者
Luconi, Lapo [1 ]
Klosin, Jerzy [2 ]
Smith, Austin J. [2 ]
Germain, Stephane [3 ]
Schulz, Emmanuelle [3 ,4 ]
Hannedouche, Jerome [3 ,4 ]
Giambastiani, Giuliano [1 ]
机构
[1] Inst Chem OrganoMetall Cpds ICCOM CNR, I-50019 Florence, Italy
[2] Dow Chem Co USA, Corp R&D, Midland, MI 48674 USA
[3] Univ Paris 11, ICMMO, UMR 8182, Equipe Catalyse Mol, F-91405 Orsay, France
[4] CNRS, F-91405 Orsay, France
关键词
INTRAMOLECULAR HYDROAMINATION; ASYMMETRIC HYDROAMINATION; AMIDATE COMPLEXES; LIGAND PRECURSORS; METAL-COMPLEXES; ZIRCONIUM; REACTIVITY; HAFNIUM; CRYSTAL; ACTIVATION;
D O I
10.1039/c3dt51620b
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
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 s-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.
引用
收藏
页码:16056 / 16065
页数:10
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