Issue 46, 2013
From the journal:

Dalton Transactions

Synthesis of β-diketiminate-ligated bimetallic and monometallic lanthanide amide complexes and their reactivity with isoprene and AlMe3†

Song Sun,ab   Hao Ouyang,a   Yunjie Luo,*c   Yong Zhang,a   Qi Shena  and  Yingming Yao*a  

* Corresponding authors

a Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Dushu Lake Campus, Soochow University, Suzhou 215123, People's Republic of China
E-mail: yaoym@suda.edu.cn
Fax: +(86) 512-65880305
Tel: +(86) 512-65882806

b Institute of Functional Material, School of Materials Science and Engineering, Shaanxi University of Technology, Hanzhong 723003, People's Republic of China

c Organometallic Chemistry Laboratory, Ningbo Institute of Technology, Zhejiang University, Ningbo 315100, P. R. China
E-mail: lyj@nit.zju.edu.cn

Abstract

The amine elimination of lanthanide tris(amide) complexes with the phenylene-bridged bis(β-diketiminate) ligands PARAMe-H2, METAMe-H2 and PARAPr-H2 (PARAMe-H2 = 2[2,6-Me2C6H3NHC(Me)C(H)C(Me)N]-(para-phenylene), METAMe-H2 = 2[2,6-Me2C6H3NHC(Me)C(H)C(Me)N]-(meta-phenylene), PARAPr-H2 = 2[2,6-iPr2C6H3NHC(Me)C(H)C(Me)N]-(para-phenylene)), and the mono-β-diketiminate ligand L2,6-iPr2Ph-H (2,6-iPr2C6H3)NHC(Me)CHC(Me)N(C6H5)) afforded the bimetallic lanthanide amide complexes PARAMe-{Ln[N(SiMe3)2]2}2 (Ln = Y (1), Sm (2)), METAMe-{Y[N(SiMe3)2]2}2 (3), PARAPr-{Ln[N(HSiMe2)2]2}2 (Ln = Y (4), Sm (5)), and the monomeric complexes L2,6-iPr2Ph-Y[N(SiMe3)2]2 (6) and L2,6-iPr2Ph-Y[N(HSiMe2)2]2 (7). In the presence of AlR3 and on activation with 1 equiv. of [Ph3C][B(C6F5)4], complexes 1–7 showed a high activity toward the 1,4-selective polymerization of isoprene. The heterometallic Y/Al methyl complex [L2,6-iPr2Ph]Y[(μ-Me)2AlMe2]2 (8) was prepared to elucidate the real active precursor in the polymerization.

Graphical abstract: Synthesis of β-diketiminate-ligated bimetallic and monometallic lanthanide amide complexes and their reactivity with isoprene and AlMe3

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Article information

DOI
https://doi.org/10.1039/C3DT52014E
Article type
Paper
Submitted
24 Jul 2013
Accepted
09 Sep 2013
First published
09 Sep 2013

Dalton Trans., 2013,42, 16355-16364

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Synthesis of β-diketiminate-ligated bimetallic and monometallic lanthanide amide complexes and their reactivity with isoprene and AlMe3

S. Sun, H. Ouyang, Y. Luo, Y. Zhang, Q. Shen and Y. Yao, Dalton Trans., 2013, 42, 16355 DOI: 10.1039/C3DT52014E

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