文献类型：期刊文献

英文题名：A robust chromium-diphosphine catalyst for high temperature ethylene tri-/tetramerization

作者：Liu, Dongchang[1,2];Zhao, Xing[1,2];Huang, Zuoxin[1,2];Zhang, Zhihao[1,2];Cui, Shicong[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, Sch Chem & Mol Engn, 130 Mei Long Rd, Shanghai 200237, Peoples R China

年份：2026

卷号：459

外文期刊名：JOURNAL OF CATALYSIS

收录：;EI(收录号：20261820646057);WOS:【SCI-EXPANDED(收录号:WOS:001762817100001)】；

基金：Financial support from the Fundamental Research Funds for the Central Universities (222201717003) , and the National Natural Science Foundation of China (22071055) is greatly acknowledged.

语种：英文

外文关键词：Ethylene trimerization; Ethylene tetramerization; Backbone-disubstituted ligand; Diphosphine ligand; Chromium(III) catalysts

摘要：This study presents an efficient and modular synthetic strategy for the preparation of a series of novel backbonedisubstituted diphosphinoethene ligands (dpen) of the PCCP-type (PPh2(R1)C=C(R2)PR3R4). This synthetic strategy employs a key coupling reaction between functionalized organocopper(I) intermediates and chlorophosphines, which uniquely enables structural diversification at the backbone positions of ethylene-bridged PCCP ligands in addition to the phosphorus centers. When applied in chromium-catalyzed ethylene tri-/tetramerization, these backbone-disubstituted dpen ligands demonstrated significantly enhanced catalytic performance compared to the backbone-mono-substituted dpen and phenylene-bridged dppbz ligands. In particular, the ligand Ph2P(Ph)C=C(Et)PPh2 (L2) exhibited exceptional activity (up to 4874 kg center dot gCr-1 center dot h-1) and high combined 1-hexene/1-octene selectivity (89 wt%) at very low catalyst loading (0.25 mu mol), while also maintaining remarkable thermal stability (4728 kg center dot gCr-1 center dot h-1 at 120 degrees C; 3097 kg center dot gCr-1 center dot h-1 at 140 degrees C). Systematic structure-activity relationship studies revealed that steric parameters, quantified by percent buried volume (%Vbur), positively correlate with catalytic activity. This work provides valuable insights into ligand design for selective tri-/tetramerization and offers a new family of highly tunable diphosphine ligands with strong potential for industrial application.