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A chromium precursor for the Phillips ethylene trimerization catalyst: (2-ethylhexanoate)2CrOH†
Jong Yeob Jeon,Dong Sik Park,Dong Hwan Lee,Seong Chan Eo,Seong Yeon Park,Myoung Sun Jeong,Yi Young Kang,Junseong Lee,Bun Yeoul Lee
Dalton Transactions Pub Date : 05/05/2015 00:00:00 , DOI:10.1039/C5DT01203A
Abstract

The conventional Phillips ethylene trimerization catalyst prepared by reacting Cr(EH)3 (EH = 2-ethylhexanoate), 2,5-dimethylpyrrole (Me2C4H2NH), Et3Al, and Et2AlCl in an aromatic hydrocarbon solvent was improved to obtain a congener composed of a new chromium precursor (EH)2CrOH, (Me2C4H2N)AlEt2, and Et3Al·ClAlEt2. Reaction of CrCl3 with 3 equiv. Na(EH) in water did not generate Cr(EH)3, but unexpectedly produced (EH)2CrOH. In comparison with the erratic catalytic performance of the original Phillips system, due to the ill-defined nature of the Cr(EH)3 source (16 or 6.8 × 106 g per mol-Cr h depending on the source), the improved system exhibited consistently high activity (54 × 106 g per mol-Cr h). Reaction of (EH)2CrOH with (Me2C4H2N)AlMe2·OEt2 afforded the dimeric Cr(II)-complex (6) coordinated by (η5-Me2C4H2N)AlMe2(NC4H2Me2) and μ2–κ12-Me2C4H2N ligands. 6 provided highly active species when activated with Et3Al·ClAlEt2.

Graphical abstract: A chromium precursor for the Phillips ethylene trimerization catalyst: (2-ethylhexanoate)2CrOH
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