NDLI: Synthesis of vanadium(III) complexes bearing iminopyrrolyl ligands and their role as thermal robust ethylene (co)polymerization catalysts

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Mu, Jing-shan Li, Yue-sheng Wang, Yong-xia Li, Bai-xiang
Description	Author Affiliation: Mu JS ( State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022, China.)
Abstract	Bis(imino)pyrrolyl vanadium(III) complexes 2a–e $[2,5-C_{4}H_{2}N(CH=NR)_{2}]VCl_{2}(THF)_{2}$ [R = $C_{6}H_{5}$ (2a), $2,6-Me_{2}C_{6}H_{3}$ (2b), $2,6-^{i}Pr_{2}C_{6}H_{3}$ (2c), $2,4,6-Me_{3}C_{6}H_{2}$ (2d), $C_{6}F_{5}$ (2e)] and bis(iminopyrrolyl) vanadium(III) complex 4f $[C_{4}H_{3}N(CH=N-2,6-^{i}PrC_{6}H_{3})]_{2}VCl(THF)$ have been prepared in good yields from $VCl_{3}(THF)_{3}$ by treating with 1.0 and 2.0 equivalent deprotonated ligands in tetrahydrofuran (THF), respectively. These complexes were characterized by FTIR and mass spectra as well as elemental analysis . Structures of 2c and 4f were further confirmed by X-ray crystallographic analysis . DFT calculations indicated the configurations of 2a–e with two nitrogen atoms of the chelating ligand coordinating with vanadium metal centre were more stable in energy. These complexes were employed as catalysts for ethylene polymerization at various reaction conditions. On activation with $Et_{2}AlCl,$ these complexes exhibited high catalytic activities (up to 22.2 kg $mmol^{−1}_{V}$ $h^{−1}bar^{−1})$ even at high temperature, suggesting these catalysts possessed remarkable thermal stability. Moreover, high molecular weight polymer with unimodal molecular weight distributions can be obtained, indicating the polymerization took place in a single-site nature. The copolymerizations of ethylene and 1-hexene with precatalysts 2a–e and 4f were also explored in the presence of $Et_{2}AlCl.$ Catalytic activity, comonomer incorporation, and properties of the resultant polymers can be controlled over a wide range by tuning catalyst structures and reaction parameters.
ISSN	14779226
Issue Number	14
Journal	Dalton Trans.
Volume Number	40
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2011-04-14
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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