Extremely Active Ethylene Tetramerization Catalysts [iPrN（PAr2）2–CrCl2][B（C6F5）4] Bearing Long-Alkyl R3Si Substituents : Scale-Up Synthesis and Substituent Effects
- 주제(키워드) chromium catalyst , bis（phosphine） ligand , tetrakis（pentafluorophenyl）borate , ethylene tetramerization , 1-octene production
- 주제(DDC) 547
- 발행기관 아주대학교 일반대학원
- 지도교수 이분열
- 발행년도 2026
- 학위수여년월 2026. 8
- 학위명 석사
- 학과 및 전공 일반대학원 분자과학기술학과
- 실제URI http://www.dcollection.net/handler/ajou/000000036152
- 본문언어 영어
- 저작권 아주대학교 논문은 저작권에 의해 보호받습니다.
초록/요약
In response to a request for kilogram-scale synthesis of the highly active ethylene tetramerization catalyst [iPrN（PAr2）2–CrCl2][B（C6F5）4] （Ar = C6H4-p-Si（octyl）3）, a shortened synthetic route to the ligand iPrN（PAr2）2 was developed. p- ClC6H4Si（octyl）3 was efficiently synthesized in a one-pot procedure from readily available 1-chlorooctane using Mg, SiCl4, and p-ClC6H4MgBr. Subsequent conversion to the corresponding Grignard reagent, ClMgC6H4-p-Si（octyl）3, followed by reaction with iPrN（PCl2）2, afforded the desired PNP ligand. This new synthetic route enabled the preparation of a series of ligands, iPrN[P（C6H4-p-SiR3）2]2 （R = decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl）, which could not be accessed by the previously reported synthetic method developed for the octyl analogue. The corresponding chromium complexes, [iPrN（PAr2）2–CrCl2][B（C6F5）4], were evaluated in ethylene tetramerization. The complex bearing -Si（decyl）3 substituents exhibited catalytic activity 1.5 times higher than that of the parent -Si（octyl）3 analogue, while also providing slightly improved selectivity toward 1-octene and suppressing the formation of undesired cyclic-C6 and polyethylene byproducts. KEYWORDS: chromium catalyst, bis（phosphine） ligand, tetrakis（pentafluorophenyl）borate, ethylene tetramerization, 1-octene production
more목차
1. Introduction 1
2. Results and Discussion 3
2.1 Up-scaling Synthesis of iPrN[P（C6H4-p-SiR3）2]2 （R = octyl） （1） 3
2.2 Synthesis of iPrN[P（C6H4-p-SiR3）2]2 Bearing Longer Alkyl Chains 5
2.3 Preparation of Chromium Catalysts 9
2.4 Oligomerization Studies. 10
3. Experimental Section 13
3.1 p-ClC6H4Si（octyl）3 13
3.2 iPrN[P（C6H4-p-SiR3）2]2 （R = octyl） （1） 14
3.3 Preparation of [1−CrCl2][B（C6F5）4] 15
4. Conclusions 15
5. Acknowledgments 16
6. References 16
7. Supporting information 21
