文献类型：期刊文献

英文题名：DivergentSynthesis of Thiophene-Bridged DiphosphineLigands and Their Application in Chromium-Catalyzed Ethylene Tri-/Tetramerization

作者：Zuo, Jing[1,2];Du, Wenbin[1,2];Wu, Chenqing[1,2];Liu, Dongchang[1,2];Zhao, Xing[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, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Inst Fine Chem, Sch Chem & Mol Engn, Shanghai 200237, Peoples R China

年份：2026

卷号：45

期号：14

起止页码：1746

外文期刊名：ORGANOMETALLICS

收录：;EI(收录号：20263121207064);Scopus(收录号：2-s2.0-105046009316);WOS:【SCI-EXPANDED(收录号:WOS:001824445900001)】；

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：Catalyst activity - Catalyst selectivity - Chelation - Chromium compounds - Ligands - Synthesis (chemical) - Thiophene

摘要：Chromium complexes supported by tunable thiophene-bridged diphosphine ligands demonstrate exceptional catalytic activity with switchable selectivity in ethylene tri/tetramerization reactions. The catalytic performance was significantly influenced by the synergistic interplay of steric effects from both the P substituents and the thiophene backbone substituents. Complex Cr2, bearing a PCy2 group, achieved a high activity of 1549 kg/(gCr & centerdot;h) with excellent total 1-C6/1-C8 selectivity (90.6 wt %) and low PE content (0.34 wt %) at 60 degrees C. Complex Cr4 having a TMS-substituted backbone and one Cy on the P atom achieved the highest activity of 2139 kg/(gCr & centerdot;h) at 80 degrees C, maintained considerable 1-C8 selectivity (28.1 wt %), and yielded a very low amount of PE (0.24 wt %). However, Cr3 having two steric bulk PCy2 groups exhibited a decreased activity. The findings underscore the necessity for moderate steric tuning and the significant regulatory role of backbone substituents. Some of the new complexes are among the most efficient ethylene tri/tetramerization catalysts. This work offers a novel family of highly tunable diphosphine ligands, providing valuable insights into the rational ligand design for selective ethylene oligomerization.