Synthesis and application of chromium complexes based on 4,5-bis(diphenylphosphanyl)-H-1,2,3-triazole ligands to obtain higher С10–С18 olefins

A. A. Senin, K. B. Polyanskii, A. M. Sheloumov, V. V. Afanasiev, T. M. Yumasheva, K. B. Rudyak, S. V. Vorobyev
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Abstract

Objectives. To synthesize 4,5-bis(diphenylphosphanyl)-H-1,2,3-triazole ligands and new chromium complexes based on them, in order to obtain a fraction of higher C10–C18 alpha-olefins from ethylene.Methods. The Schlenk technique was used to obtain the target chromium complexes. Diphenylphosphanyl triazole ligands can be characterized by nuclear magnetic resonance spectroscopy. The composition of the final products was confirmed by elemental analysis. The liquid phase of the oligomerization reaction was studied by gas chromatography.Results. L1–L9 ligands were obtained, and K1–K9 chromium complexes were synthesized based on the correspondent ligands using commercially available chromium (III) trichloride tris(tetrahydrofuran). The K1–K9 complexes thus obtained were tested in the process of ethylene oligomerization.Conclusions. Chromium complexes based on 4,5-bis(diphenylphosphanyl)-H-1,2,3-triazoles K1–K9 were produced in high yields using the Schlenk technique. It was found that systems based on the K4–K7 and K9 complexes enable the ethylene oligomerization process to be carried out with a sufficiently high level of productivity. It was shown that the introduction of a dialkyl zinc derivative increases the performance and selectivity of the catalytic system for the target fraction.
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基于 4,5-双(二苯基膦酰基)-H-1,2,3-三唑配体的铬配合物的合成与应用,以获得更高的С10-С18 烯烃
研究目的合成 4,5-双(二苯基膦酰基)-H-1,2,3-三唑配体和以其为基础的新铬络合物,以便从乙烯中获得一部分较高的 C10-C18 α-烯烃。采用 Schlenk 技术获得目标铬络合物。二苯基膦酰基三唑配体可通过核磁共振光谱进行表征。最终产品的成分通过元素分析得到确认。通过气相色谱法研究了低聚反应的液相。利用市售的三氯化三(四氢呋喃)铬 (III) 合成了基于相应配体的 K1-K9 铬配合物。由此获得的 K1-K9 复合物在乙烯低聚过程中进行了测试。利用 Schlenk 技术高产制得了基于 4,5-双(二苯基膦酰基)-H-1,2,3-三唑 K1-K9 的铬络合物。研究发现,以 K4-K7 和 K9 复合物为基础的系统能够以足够高的生产率进行乙烯低聚过程。研究表明,引入二烷基锌衍生物可提高催化系统对目标馏分的性能和选择性。
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