이분열 이춘선 2015-02 18874 https://aurora.ajou.ac.kr/handle/2018.oak/12673 학위논문(석사)--아주대학교 일반대학원 :분자과학기술학과,2015. 2 Abstract 1. Introduction 2. Results and discussion 2. 1 Ligand synthesis 2. 2 Metalation reaction 2. 3 X-ray crystallographic studies 2. 4 Polymerization studies 2.5 Conclusion 3. Experimental section 3. 1 General remarks 3. 2 Synthesis of ligands and complexes 3. 3 Typical procedure for ethylene/1-octene copolymerization (entry 3 in Table 1) 3. 4 X-ray crystallography 4. Acknowledgments 5. Reference 6. Supporting information eng The Graduate School, Ajou University 아주대학교 논문은 저작권에 의해 보호받습니다. 비스(아마이도)-포스핀, [아마이도-포스핀 설파이드] 지르코늄 및 하프늄 화합물 합성 및 이를 이용한 올레핀 중합 Chun Sun Lee Thesis 아주대학교 일반대학원 Chun Sun Lee 일반대학원 분자과학기술학과 2015. 2 Master http://dcoll.ajou.ac.kr:9080/dcollection/jsp/common/DcLoOrgPer.jsp?sItemId=000000018874 New phosphine-based bidentate ligands, 2-Me-8-Ph2P(X)C9H8NH (3, X = O; 4, X = S) and N-R-2-Ph2P(X)C6H4NH (5, R = Et, X = O; 6, R = Me, X = S; 7, R = Et, X = S) were prepared via ortho-lithiation of 1,2,3,4-tetrahydroquinaldine (2-Me-C9H9NH) and aniline derivatives (N-R-C6H5NH). Reaction of the ortho-lithiated compounds with 0.5 equiv of PhP(OPh)2 afforded the bis(amido)-phosphine ligands (2-Me-C9H8NH-8-yl)2PPh 8 and (N-R-C6H4NH-2-yl)2PPh (9, R = Me; 10, R = Et). Using these ligands, [amido-phosphine oxide]Hf(CH2Ph)3, [amido-phosphine sulfide]Hf(CH2Ph)3, [bis(amido)-phosphine]MX2 (M = Hf, Zr; X = CH2Ph, Cl, Me), and [amido-phosphine-amine]MCl3 complexes were prepared. The molecular structures of [amido-phosphine sulfide]Hf(CH2Ph)3 13 (prepared using 6), [bis(amido)-phosphine]ZrMe2 22 (prepared using 8), and [amido-phosphine-amine]MCl3 (23, M = Hf; 24, M = Zr; prepared using 9) were confirmed by X-ray crystallography. Most of the prepared complexes exhibited negligible or low activity for ethylene/1-octene copolymerization. The [amido-phosphine sulfide]Hf(CH2Ph)3 complex 13 exhibited relatively high copolymerization activity (19  106 g/mol-Hf•h); however, this activity was unsatisfactory compared to that of the related [amido-phosphine]Hf(CH2Ph)3 complexes (up to 48  106 g/mol-Hf•h).