后茂金属镧系氢化物化学：由胍基配体支持的新型配合物[{Ln{(Me3Si)2NC(NiPr)2}2(μ-H)}2]（Ln = Y、Nd、Sm、Gd、Yb）——烯烃聚合中的合成、结构及催化活性

Postmetallocene lanthanide-hydrido chemistry: A new family of complexes [{Ln{(Me3Si)2NC(NiPr)2}2(mu-H)}2] (Ln = Y, Nd, Sm, Gd, Yb) supported by guanidinate ligands-synthesis, structure, and catalytic activity in olefin polymerization.

作者信息

Trifonov Alexander A, Skvortsov Grigorii G, Lyubov Dmitrii M, Skorodumova Nina A, Fukin Georgii K, Baranov Evgenii V, Glushakova Valentina N

机构信息

G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, Tropinia 49, 603600 Nizhny Novgorod GSP-445, Russia.

出版信息

Chemistry. 2006 Jul 5;12(20):5320-7. doi: 10.1002/chem.200600058.

DOI:10.1002/chem.200600058

PMID:16680789

Abstract

The new family of Lewis base free hydrido complexes of rare-earth metals supported by guanidinate ligands [{Ln{(Me3Si)2NC(NiPr)2}2(mu-H)}2] (Ln = Y, Nd, Sm, Gd, Yb) was synthesized and structurally characterized. Single-crystal X-ray and solution NMR studies revealed that these complexes are dimeric in both solid state and in [D6]benzene. The dimeric hydrido complexes can adopt eclipsed (Nd, Sm, Gd) or staggered (Y, Yb, Lu) conformations depending on the metal-atom size. Catalytic activity of these [{Ln{(Me3Si)2NC(NiPr)2}2(mu-H)}2] complexes in the polymerization of ethylene, propylene, and styrene has been investigated. Complexes of Sm and Y have high catalytic activity in ethylene polymerization (1268 and 442 g mmol(-1) atm(-1) h(-1), respectively).

摘要

合成并通过结构表征得到了由胍基配体支撑的新型无路易斯碱稀土金属氢化物配合物[{Ln{(Me3Si)2NC(NiPr)2}2(μ-H)}2]（Ln = Y、Nd、Sm、Gd、Yb）。单晶X射线和溶液核磁共振研究表明，这些配合物在固态和[D6]苯中均为二聚体。根据金属原子大小，二聚体氢化物配合物可采取重叠式（Nd、Sm、Gd）或交错式（Y、Yb、Lu）构象。研究了这些[{Ln{(Me3Si)2NC(NiPr)2}2(μ-H)}2]配合物在乙烯、丙烯和苯乙烯聚合反应中的催化活性。Sm和Y的配合物在乙烯聚合反应中具有高催化活性（分别为1268和442 g mmol(-1) atm(-1) h(-1)）。