Syntheses and Characterizations, and Polymerization of Novel Transition Metal Complexe
새로운 전이금속화합물의 합성 및 이를 이용한 중합
- 발행기관 亞州大學校 大學院
- 지도교수 李汾烈
- 발행년도 2005
- 학위수여년월 2005. 2
- 학위명 석사
- 학과 및 전공 대학원 공학계열
- 본문언어 영어
초록/요약
1. Addition of primary amines to N-[2-(diphenylphosphanyl)benzoyloxy]succinimide affords 2-diphenylphosphanylbenzamides, Ph₂PC_(6)H₄C(O)NHR (R = C(CH₃)₃, 3; R = H, 4; R = CH₂CH₂CH, 5; R = CH(CH₃)₂, 6). Addition of NiCl(η³-CH₂C_(6)H_(5))(PMe₃) to the deprotonated potassium salts of the amides and subsequent treatment of 2 equivalents of B(C_(6)F_(5))3 to the resulting products furnish η³-benzyl zwitterionic nickel(Ⅱ) complexes, [Ph₂PC_(6)H₄C(O)NR-κ²N,P]Ni(η³-CH₂C_(6)H_(5)) (R = C_(6)H_(5), 9; R = C(CH₃)₃, 10; R = H, 11; R = CH₂CH₂CH₃, 12; R = CH(CH₃)₂, 13). Solid structures of 9, 11, 13, and the intermediate η¹-benzyl nickel(Ⅱ) complexes, [Ph₂PC_(6)H₄C(O)NR-κ²N,P]Ni(η¹-CH₂C_(6)H_(5))(PMe₃) (R = C_(6)H_(5), 7; R = C(CH₃)₃, 8) were determined by x-ray crystallography. When ethylene is added to the η³-benzyl zwitterionic nickel(Ⅱ) complexes, butene is obtained by the complexes 9 - 12 but complex 13 provides very high molecular-weight branched polyethylene (Mw, ~1,300,000) with excellent activity (up to 5,200 Kg/mol?h at 100 psig). 2. The Schiff's base condensation of 1-3 with 2-fluorobenzaldehyde and subsequent nucleophilic substitution of the fluoride with (2,6-R'₂C_(6)H₃)N(H)Li affords ortho-phenylene bridged bis(anilido-aldimine) compounds, ortho-C_(6)H₄{C_(6)H₂R₂N=CH-C_(6)H₄-(H)N(C_(6)H₃R'₂)}₂ (R = iPr, R' = iPr, 7; R = Et, R' = Et, 8; R = Me, R' = Me, 9; R = Me, R' = iPr, 10; R = Et, R' = Me, 11; R = Et, R' = iPr, 12; R = iPr, R' = Et, 13). The molecular structure of 9 is confirmed by X-ray crystallography. Dinuclear μ-methylsulfinato zinc complexes, ortho-C_(6)H₄{(C_(6)H₂R₂N=CH-C_(6)H₄-N(C_(6)H₃R'₂)-κ²N,N)Zn(μ-OS(O)Me)}₂ (R = iPr, R' = iPr, 14; R = Et, R' = Et, 15; R = Me, R' = Me, 16; R = Me, R' = iPr, 17; R = Et, R' = Me, 18; R = Et, R' = iPr, 19; R = iPr, R' = Et, 20) are prepared almost quantitatively by successive addition of Me₂Zn and SO₂gas to the corresponding anilido-aldimine compounds. Molecular structures of 19 is confirmed by X-ray crystallography. Complexes 15 and 16 show high activity for cyclohexene oxide/CO₂copolymerization at low [Zn]/[monomer] ratio (1:5600) whereas the β-diketiminato complex {[(C_(6)H₃Et₂)N=C(Me)CH=C(Me)N(C_(6)H₃Et₂)]Zn(μ-OS(O)Et)}₂ shows negligible activity in the same condition. Activity is sensitive to the N-aryl ortho-substituents and the highest activity is observed with 17 bearing methyl and isopropyl substituents. Turn over number up to 2980 and molecular weight (Mn) up to 284000 are attained with 17 at such a highly diluted condition as [Zn]/[monomer] = 1:17400.
more초록/요약
1. N-[2-(diphenylphosphanyl)benzoyloxy]succinimide 화합물을 1차 아민과 반 시켜 2-diphenylphosphanylbenzamides, Ph₂PC_(6)H₄C(O)NHR (R = C(CH₃)₃,3; R = H, 4; R = 4; R = CH₂CH₂CH, 5; R = CH(CH₃)₂,6). Addition of NiCl(η³-CH₂C_(6)H_(5))(PMe₃) 화합물을 합성한다. KH를 사용하여 deprotonation 반응을 하여 얻어진 amide salts 화합물을 NiCl(η³-CH₂C_(6)H_(5))(PMe₃)와 반응시키고, 그 후 2당량의 B(C_(6)F_(5))3를 반응시켜 η₃-benzyl zwitterionic nickel(Ⅱ) 화합물을 합성하였다. [Ph₂PC_(6)H₄C(O)NR-κ²N,P]Ni(η³-CH₂C_(6)H_(5)) (R = C_(6)H_(5), 9; R = C(CH₃)₃, 10; R = H, 11; R = CH₂CH₂CH₃, 12; R = CH(CH₃)₂, 13). 화합물 9, 11, 13과 η₃-benzyl nickel(II) 화합물 [Ph₂PC_(6)H₄C(O)NR-κ²N,P]Ni(η¹-CH₂C_(6)H_(5))(PMe₃) (R = C_(6)H_(5), 7; R = C(CH₃)₃, 8)의 구조는 x-ray crystallog raphy로 결정되어졌다. 9-12 η₃-benzyl zwitterionic nickel(II) 화합물로 에틸렌 중합을 한 결과, 부텐이 생성되었지만, 13 화합물은 고분자량의 branched 폴리에틸렌 (Mw, ~1,300,000)을 고활성 (100 psig 에서5,200 Kg/mol×h 이상)으로 생성하였다. 2. 화합물 1-3 과 2-fluorobenzaldehyde 와의 Schiff’s condensation 반응을 통해 얻어진 화합물 4-6 와 fluoride 에 대해 친핵성 치환체를 가진 (2,6-R'₂C_(6)H₃)N(H)Li 화합물의 반응을 통해 ortho-phenylene bridged bis(anilido-aldimine) 화합물, ortho-C_(6)H₄{C_(6)H₂R₂N=CH-C_(6)H₄-(H)N(C_(6)H₃R'₂)}₂ (R = iPr, R' = iPr, 7; R = Et, R' = Et, 8; R = Me, R' = Me, 9; R = Me, R' = iPr, 10; R = Et, R' = Me, 11; R = Et, R' = iPr, 12; R = iPr, R' = Et, 13)을 합성하였다. 화합물 9의 분자구조는 Xray crystallography 에 의해 확인되었다. Dinuclear μ-methylsulfinato zinc 화합물, ortho-C_(6)H₄{(C_(6)H₂R₂N=CH-C_(6)H₄-N(C_(6)H₃R'₂)-κ²N,N)Zn(μ-OS(O)Me)}₂ (R = iPr, R' = iPr, 14; R = Et, R' = Et, 15; R = Me, R' = Me, 16; R = Me, R' = iPr, 17; R = Et, R' = Me, 18; R = Et, R' = iPr, 19; R = iPr, R' = Et, 20)은 anilido-aldimine 화합물에 Me₂Zn 와 SO₂gas 와의 반응을 통해 거의 정량적으로 합성되어졌다. 화합물 20 의 분자구조는 X-ray crystallography 에 의해 확인되었다. 화합물 15-20 은 cyclohexene oxide/CO₂공중합에 대해 낮은 [Zn]/[monomer] 비율 (1:5600)에서 고활성을 보였고, 반면에 β-diketiminato 화합물 {[(C_(6)H₃Et₂)N=C(Me)CH=C(Me)N(C_(6)H₃Et₂)]Zn(μ-OS(O)Et)}₂은 같은 조건에서 무시할만한 수준의 활성을 보였다. 활성은 N-aryl ortho-치환기에 민감하고 가장 높은 활성을 나타낸 화합물은 메틸과 이소프로필 치환기를 가진 17 이었다. 화합물 17 은 [Zn]/[monomer] = 1:17400 와 같이 적은 농도 조건에서 turn over number(TON)가 2980 이상으로 확인되었고 284000 (Mn) 이상의 고분자량의 고분자를 얻을 수 있었다.
more목차
Table of Contents
Cover page = ⅰ
Approval page = ⅱ
Acknowledgement = ⅲ
Abstract = ⅳ
Table of Contents = ⅵ
List of Figures = ⅷ
List of Tables = ⅹ
Abbreviation = xi
Chapter 1. Syntheses, Characterizations and Ethylene Reactivities of 2-Diphenylphosphanylbenzcarboxamido Nickel Complexes = 1
1-1. Introduction = 2
1-2. Syntheses and characterizations = 4
1-3. Ethylene reactivity studies = 11
1-4. Conclusion = 14
1-5. Experimental Section = 15
1-6. Crystallographic Studies = 26
1-7. Figures(7~15) = 30
1-8. References = 39
Chapter 2. Bimetallic Anilido-Aldimine Zinc Complexes for Epoxide/CO₂ Copolymerization = 42
2-1. Introduction = 43
2-2. Result and Discussion = 45
2-3. Conclusion = 56
2-4. Experimental Section = 57
2-5. Crystallographic Studies = 73
2-6. Figures(4~10) = 78
2-7. References = 85
