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通过半不稳定配体 - 金属相互作用实现有机铬烯烃聚合催化中的分子量控制。

Molecular weight control in organochromium olefin polymerization catalysis by hemilabile ligand-metal interactions.

作者信息

Mark Stefan, Wadepohl Hubert, Enders Markus

机构信息

Anorganisch-Chemisches Institut, Heidelberg University, Im Neuenheimer Feld 270, D-69120 Heidelberg, Germany.

出版信息

Beilstein J Org Chem. 2016 Jul 4;12:1372-9. doi: 10.3762/bjoc.12.131. eCollection 2016.

Abstract

A series of Cr(III) complexes based on quinoline-cyclopentadienyl ligands with additional hemilabile side arms were prepared and used as single-site catalyst precursors for ethylene polymerization. The additional donor functions interact with the metal centers only after activation with the co-catalyst. Evidence for this comes from DFT-calculations and from the differing behavior of the complexes in ethylene polymerization. All complexes investigated show very high catalytic activity and the additional side arm minimizes chain-transfer reactions, leading to increase of molecular weights of the resulting polymers.

摘要

制备了一系列基于喹啉 - 环戊二烯基配体并带有额外半不稳定侧链的Cr(III)配合物,并将其用作乙烯聚合的单中心催化剂前体。额外的供体官能团仅在与助催化剂活化后才与金属中心相互作用。这一点的证据来自密度泛函理论(DFT)计算以及这些配合物在乙烯聚合中的不同行为。所有研究的配合物都表现出非常高的催化活性,并且额外的侧链使链转移反应最小化,导致所得聚合物的分子量增加。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5dff/4979879/4ff640092e41/Beilstein_J_Org_Chem-12-1372-g005.jpg

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