Ethylene tetramerization catalyst using the cationic chromium complex

DC Field Value Language
dc.contributor.advisor이분열-
dc.contributor.author김은호-
dc.date.accessioned2018-11-08T08:10:53Z-
dc.date.available2018-11-08T08:10:53Z-
dc.date.issued2017-02-
dc.identifier.other24893-
dc.identifier.urihttps://dspace.ajou.ac.kr/handle/2018.oak/11271-
dc.description학위논문(석사)--아주대학교 일반대학원 :분자과학기술학과,2017. 2-
dc.description.tableofcontents1. Introduction 2. Results and Discussion 2.1 Preparation of cationic CrIIIcomplexes 2.2 X-ray Crystallographic Studies 2.3 Ethylene Oligomerization Studies 3. Conclusions 4. Experimental Section 4.1 General remarks 4.2 Synthesis of ligands and complexes 4.3 Typical procedure for ethylene oligomerzation 4.4 X-ray Crystallography 5. Acknowledgements 6. Reference 7. Supporting information-
dc.language.isoeng-
dc.publisherThe Graduate School, Ajou University-
dc.rights아주대학교 논문은 저작권에 의해 보호받습니다.-
dc.titleEthylene tetramerization catalyst using the cationic chromium complex-
dc.title.alternativeEun Ho Kim-
dc.typeThesis-
dc.contributor.affiliation아주대학교 일반대학원-
dc.contributor.alternativeNameEun Ho Kim-
dc.contributor.department일반대학원 분자과학기술학과-
dc.date.awarded2017. 2-
dc.description.degreeMaster-
dc.identifier.localId770230-
dc.identifier.urlhttp://dcoll.ajou.ac.kr:9080/dcollection/jsp/common/DcLoOrgPer.jsp?sItemId=000000024893-
dc.subject.keywordethylene tetramerization. cationic chromium complex-
dc.description.alternativeAbstractEthylene tetramerization catalyst composed of PNP ligand, Cr(III) complex, and MAO is useful in the production of 1-octene, in which a concern is the use of expensive MAO in excess. Herein, we report a catalytic system that avoids the use of MAO. Metathesis of CrCl3(THF)3 and [(CH3CN)4Ag]+[B(C6F5)4]- afforded [L4CrIIICl2]+[B(C6F5)4]- (L = CH3CN or THF), which was converted to [(PNP)CrCl2L2]+[B(C6F5)4]- where PNP is iPrN(PPh2)2 (1) or [CH3(CH2)16]2CHN(PPh2)2 (2). The molecular structures of [(THF)4CrIIICl2]+[B(C6F5)4]- and [1-CrCl2(THF)2]+[B(C6F5)4]- were unambiguously determined by X-ray crystallography. The cationic (PNP)CrIII complexes paired with [B(C6F5)4]- anion, i.e., [(PNP)CrCl2(CH3CN)2]+[B(C6F5)4]- exhibit high activity in chlorobenzene when activated with common trialkylaluminum (Me3Al, Et3Al, and iBu3Al). The activity and selectivity were comparable to those of the original MAO-based Sasol system (1-CrCl3/MMAO). The Cr complex [2-CrCl2(CH3CN)2]+[B(C6F5)4]- bearing long alkyl chains activated with Et3Al or iBu3Al showed high activity in more desirable methylcyclohexane solvent (89 Kg/g-Cr/h) and much higher activity in cyclohexene bearing -electrons (168 Kg/g-Cr/h). Negligible catalyst deactivation, formation of negligible amount of PE (0.3%), and formation of less amount of unwanted side products above C10 are another advantages gained by the catalytic system [2-CrCl2(CH3CN)2]+[B(C6F5)4]-/Et3Al in cyclohexene. [B(C6F5)4]- anion is compatible with trialkylaluminum in itself once it is not paired with trityl cation, and, hence, [(PNP)CrCl2(CH3CN)2]+[B(C6F5)4]-/Et3Al exhibited high activity in contrast with very low activity of the reported system composed of [Ph3C]+[B(C6F5)4]-, i.e., 1/CrCl3(THF)3/[Ph3C]+[B(C6F5)4]-/Et3Al.-
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Graduate School of Ajou University > Department of Molecular Science and Technology > 3. Theses(Master)
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