文献类型：期刊文献

英文题名：Ethylene tri-/tetramerization catalysts supported by diphosphinothiophene ligands

作者：Zhang, Chengye[1,2];Song, Liubing[1,2];Wu, Hongfei[3];Ji, Xiaoyu[1,2];Jiao, Jiajun[1,2];Zhang, Jun[1,2]

机构：[1]East China Univ Sci & Technol, Sch Chem & Mol Engn, Key Lab Adv Mat, 130 Mei Long Rd, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Inst Fine Chem, Key Lab Adv Mat, 130 Mei Long Rd, Shanghai 200237, Peoples R China;[3]SINOPEC, Beijing Res Inst Chem Ind, Yanshan Branch, Beijing 102500, Peoples R China

年份：2017

卷号：46

期号：26

起止页码：8399

外文期刊名：DALTON TRANSACTIONS

收录：;EI(收录号：20172803927252);WOS:【SCI-EXPANDED(收录号:WOS:000404860300011)】；

基金：Financial support from the National Natural Science Foundation of China (21171056 and 21671066) is greatly acknowledged.

语种：英文

外文关键词：Crystal atomic structure - Catalyst supports - Ethylene - X ray diffraction - Bond length - Catalyst activity - Synthesis (chemical) - Chromium compounds - Single crystals

摘要：Cr(III) catalysts supported by a series of diphosphinothiophene ligands have been developed, all of which, upon activation with MMAO-3A, are active for ethylene tri-/tetramerization. The effect of ligand substitution on the catalytic performance has been examined. The Cr precatalyst supported by the diphosphinothiophene ligand containing one trimethylsilyl group at the C2 position achieved a high activity of up to 686 kg (g Cr h(-1))(-1) with a total selectivity of up to 69% toward 1-hexene (29.5%) and 1-octene (39.5%). Two representative Cr complexes bearing the diphosphinothiophene ligand were synthesized and structurally characterized by single-crystal X-ray diffraction. Comparison of the coordination structure data of the two Cr complexes with those of an analogous diphosphine Cr complex reveals a direct correlation between the bond length of two adjacent bridging carbon atoms and catalytic activity: a shorter bond length and hence smaller ligand bite angle lead to higher catalytic activity. These diphosphinothiophene ligands featuring a fine-tuned backbone provide a model for the precise understanding of the impact of ligand variations on the catalytic performance.