Citation: ZHANG Gong-Ping, XI Xin, JIANG Wen-Jun, CHEN Zhi-Kang, ZHU Hong-Ping. Synthesis and Catalytic Property of Constrained Geometric Structural Metal Compounds[J]. Chinese Journal of Inorganic Chemistry, ;2020, 36(12): 2249-2260. doi: 10.11862/CJIC.2020.261 shu

Synthesis and Catalytic Property of Constrained Geometric Structural Metal Compounds

State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiamen University, Xiamen, Fujian 361005, China

Corresponding author: JIANG Wen-Jun, jiangwenj@stu.xmu.edu.cn ZHU Hong-Ping, hpzhu@xmu.edu.cn
Received Date: 28 July 2020
Revised Date: 28 September 2020

Figures(9)

Three ansa-fluorenyl-arylamino ligand compounds Me₂Si[(Flu)H]NH-2, 6-ⁱPr₂C₆H₃ (L¹), Me₂Si[2, 7-^tBu₂Flu (H)]NH-2, 6-ⁱPr₂C₆H₃ (L²) and Me₂Si[2, 7-^tBu₂Flu(H)]NH-2, 4, 6-Me₃C₆H₂) (L³) were prepared by means of selection of the suitable synthetic route and method. The reactions using L¹~L³ each with group Ⅳ MCl₄ by ⁿBuLi-lithiation followed with metathesis yielded the constrained geometric metallocene compounds [Me₂Si(Flu)(N-2, 6-ⁱPr₂C₆H₃)]ZrCl₂ (THF)₂ (1), [Me₂Si(2, 7-^tBu₂Flu)(N-2, 6-ⁱPr₂C₆H₃)]TiMe₂ (2), [Me₂Si(2, 7-^tBu₂Flu)(N-2, 4, 6-Me₃C₆H₂)]TiMe₂ (3) and [Me₂Si (2, 7-^tBu₂Flu)(N-2, 6-ⁱPr₂C₆H₃)]HfMe₂ (4). The operation for synthesis of all these compounds was conducted by using moisture-and oxygen-free Schlenk technology. Compounds L¹~L³ and 1~4 have all been characterized by NMR spectroscopy and elemental analysis, of which 1~3 further by X-ray crystallography. In combination of AlⁱBu₃ and (Ph₃C)⁺[B(C₆F₅)₄]^- as the co-catalysts, the catalytic properties of 1~4 were investigated on ethylene/1-octene polymerization. The results obtained indicate a single-site catalysis (SSC) with 1-octene copolymerized. The catalytic properties of related titanium compounds [Me₂Si(C₅Me₄)(N^tBu)]TiCl₂, [Me₂Si(Ind)(N^tBu)]TiCl₂ and [Me₂Si(Flu)(N^tBu)]TiMe₂ were also examined. The correlations between the structures of 1~4 and the catalytic property are discussed.CCDC:1975179, 1; 1975180, 2; 1986175, 3; 1986178, 5.
- ansa-fluorenyl-arylamino ligand,
- constrained geometric catalyst,
- ethylene/1-octene polymerization,
- catalytic reaction condition
1. [1]
  Shapiro P J, Bunel E, Schaefer W P, et al. Organometallics, 1990, 9:867-869 doi: 10.1021/om00117a055
2. [2]
  Fink G, Mulhaupt R, Brintzinger H H. Ziegler Catalysts:Recent Scientific Innovations and Technological Improvements. New York:Springer Verlag, 1995:511
3. [3]
  Stevens J C, Timmers F J, Wilson D R, et al. EP Patent, 0416815, 1991-03-13.
4. [4]
  (a) McKnight A L, Waymouth R M. Chem. Rev., 1998, 98: 2587-2598
  (b)McKnight A L, Masood M A, Waymouth R M, et al. Organometallics, 1997, 16: 2879-2885
  (c)Xu G, Cheng D. Macromolecules, 2001, 34: 2040-2047
  (d)Lanza G, Fragalà I L, Marks T J. Organometallics, 2002, 21: 5594-5612
5. [5]
  Joe D J, Wu C J, Bok T, et al. Dalton Trans., 2006, 25:4056-4062
6. [6]
  Xu G, Ruckenstein E. Macromolecules, 1998, 31:4724-4729 doi: 10.1021/ma980498d
7. [7]
  Klosin J, Kruper W J, Nickias P N, et al. Organometallics, 2001, 20:2663-2665 doi: 10.1021/om010016d
8. [8]
  Irwin L J, Reibenspies J H, Miller S A. J. Am. Chem. Soc., 2004, 126:16716-16717 doi: 10.1021/ja044678g
9. [9]
  Dare E O, Ogunniyi D S, Olatunji G A, et al. Bull. Chem. Soc. Ethiop., 2004, 18:131-141
10. [10]
  (a) Grandini C, Camurati I, Guidotti S, et al. Organometallics, 2004, 23: 344-360
  (b)Lee S, Park S S, Kim J G, et al. Molecules, 2017, 22: 258-273
11. [11]
  Nishii K, Hagihara H, Ikeda T, et al. J. Organomet. Chem., 2006, 691:193-201 doi: 10.1016/j.jorganchem.2005.08.027
12. [12]
  Görl C, Betthausen E, Alt H G. Polyhedron, 2016, 118:37-51 doi: 10.1016/j.poly.2016.07.033
13. [13]
  Ihara E, Young V G, Jordan R F. J. Am. Chem. Soc., 1998, 120:8277-8278 doi: 10.1021/ja9817444
14. [14]
  Sheldrick G M. SHELXS-97, Program for the Solution of Crystal Structure, University of Göttingen, Germany, 1997.
15. [15]
  Sheldrick G M. SHELXL-97, Program for the Refinement of Crystal Structure, University of Göttingen, Germany, 1997.
16. [16]
  Eppinger J, Spiegler M, Hieringer W, et al. J. Am. Chem. Soc., 2000, 122:3080-3096 doi: 10.1021/ja992786a
17. [17]
  Alt H G, Föttinger K, Milius W. J. Organomet. Chem., 1999, 572:21-30 doi: 10.1016/S0022-328X(98)00527-0
18. [18]
  Okuda J, Schattenmann F J, Wocadlo S, et al. Organometallics, 1995, 14:789-795 doi: 10.1021/om00002a028
19. [19]
  Razavi A, Thewalt U. J. Organomet. Chem., 2001, 621:267-276 doi: 10.1016/S0022-328X(00)00863-9
20. [20]
  Chai J F, Abboud K A, Miller S A. Dalton Trans., 2013, 42:9139-9147 doi: 10.1039/c3dt50163a
21. [21]
  Schmid M A, Alt H G, Milius W. J. Organomet. Chem., 1997, 541:3-7 doi: 10.1016/S0022-328X(96)06471-6
22. [22]
  Sun Y J, Xu B, Shiono T. Organometallics, 2017, 36:3009-3012 doi: 10.1021/acs.organomet.7b00415
23. [23]
  Tanaka R, Yanase C, Cai Z G, et al. J. Organomet. Chem., 2016, 804:95-100 doi: 10.1016/j.jorganchem.2015.12.028
24. [24]
  Cai Z G, Ikeda T, Akita M, et al. Macromolecules, 2005, 38:8135-8139 doi: 10.1021/ma050898i
25. [25]
26. [26]
  WANG Ke-Qiang, HUANG Hong-Hong. Petrochemical Technology, 1994, 23(9):603-606
27. [27]
  (a) Kaminsky W, Noll A. Polym. Bull., 1993, 31: 175-182
  (b)Kaminsky W, Florian R. Makromol. Chem. Rapid Commun., 1993, 14: 239-243
28. [28]
  Kravchenko R, Waymouth R M. Macromolecules, 1998, 31:1-6 doi: 10.1021/ma971037f
29. [29]
  Kaminsky W. J. Chem. Soc. Dalton Trans., 1998, 9:1413-1418
30. [30]
  Wu C J, Nayab S, Woo H Y, et al. Polyhedron, 2014, 67:199-204 doi: 10.1016/j.poly.2013.08.072
31. [31]
  Park J H, Do S H, Cyriac A, et al. Dalton Trans., 2010, 39:9994-10002 doi: 10.1039/c0dt00637h
1. [1]
  Heng Zhang . Determination of All Rate Constants in the Enzyme Catalyzed Reactions Based on Michaelis-Menten Mechanism. University Chemistry, 2024, 39(4): 395-400. doi: 10.3866/PKU.DXHX202310047
2. [2]
  Yuanyin Cui , Jinfeng Zhang , Hailiang Chu , Lixian Sun , Kai Dai . Rational Design of Bismuth Based Photocatalysts for Solar Energy Conversion. Acta Physico-Chimica Sinica, 2024, 40(12): 2405016-. doi: 10.3866/PKU.WHXB202405016
3. [3]
  Dan Li , Hui Xin , Xiaofeng Yi . Comprehensive Experimental Design on Ni-based Catalyst for Biofuel Production. University Chemistry, 2024, 39(8): 204-211. doi: 10.3866/PKU.DXHX202312046
4. [4]
  Shuang Yang , Qun Wang , Caiqin Miao , Ziqi Geng , Xinran Li , Yang Li , Xiaohong Wu . Ideological and Political Education Design for Research-Oriented Experimental Course of Highly Efficient Hydrogen Production from Water Electrolysis in Aerospace Perspective. University Chemistry, 2024, 39(11): 269-277. doi: 10.12461/PKU.DXHX202403044
5. [5]
  Wen YANG , Didi WANG , Ziyi HUANG , Yaping ZHOU , Yanyan FENG . La promoted hydrotalcite derived Ni-based catalysts: In situ preparation and CO₂ methanation performance. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 561-570. doi: 10.11862/CJIC.20230276
6. [6]
  Zhiquan Zhang , Baker Rhimi , Zheyang Liu , Min Zhou , Guowei Deng , Wei Wei , Liang Mao , Huaming Li , Zhifeng Jiang . Insights into the Development of Copper-based Photocatalysts for CO₂ Conversion. Acta Physico-Chimica Sinica, 2024, 40(12): 2406029-. doi: 10.3866/PKU.WHXB202406029
7. [7]
  Jiapei Zou , Junyang Zhang , Xuming Wu , Cong Wei , Simin Fang , Yuxi Wang . A Comprehensive Experiment Based on Electrocatalytic Nitrate Reduction into Ammonia: Synthesis, Characterization, Performance Exploration, and Applicable Design of Copper-based Catalysts. University Chemistry, 2024, 39(6): 373-382. doi: 10.3866/PKU.DXHX202312081
8. [8]
  Yinuo Wang , Siran Wang , Yilong Zhao , Dazhen Xu . Selective Synthesis of Diarylmethyl Anilines and Triarylmethanes via Multicomponent Reactions: Introduce a Comprehensive Experiment of Organic Chemistry. University Chemistry, 2024, 39(8): 324-330. doi: 10.3866/PKU.DXHX202401063
9. [9]
  Qiangqiang SUN , Pengcheng ZHAO , Ruoyu WU , Baoyue CAO . Multistage microporous bifunctional catalyst constructed by P-doped nickel-based sulfide ultra-thin nanosheets for energy-efficient hydrogen production from water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1151-1161. doi: 10.11862/CJIC.20230454
10. [10]
  Yanan Liu , Yufei He , Dianqing Li . Preparation of Highly Dispersed LDHs-based Catalysts and Testing of Nitro Compound Reduction Performance: A Comprehensive Chemical Experiment for Research Transformation. University Chemistry, 2024, 39(8): 306-313. doi: 10.3866/PKU.DXHX202401081
11. [11]
  Jingzhao Cheng , Shiyu Gao , Bei Cheng , Kai Yang , Wang Wang , Shaowen Cao . 4-氨基-1H-咪唑-5-甲腈修饰供体-受体型氮化碳光催化剂的构建及其高效光催化产氢研究. Acta Physico-Chimica Sinica, 2024, 40(11): 2406026-. doi: 10.3866/PKU.WHXB202406026
12. [12]
  Wenlong LI , Xinyu JIA , Jie LING , Mengdan MA , Anning ZHOU . Photothermal catalytic CO₂ hydrogenation over a Mg-doped In₂O_3-x catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 919-929. doi: 10.11862/CJIC.20230421
13. [13]
  Kun WANG , Wenrui LIU , Peng JIANG , Yuhang SONG , Lihua CHEN , Zhao DENG . Hierarchical hollow structured BiOBr-Pt catalysts for photocatalytic CO₂ reduction. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1270-1278. doi: 10.11862/CJIC.20240037
14. [14]
  Yingchun ZHANG , Yiwei SHI , Ruijie YANG , Xin WANG , Zhiguo SONG , Min WANG . Dual ligands manganese complexes based on benzene sulfonic acid and 2, 2′-bipyridine: Structure and catalytic properties and mechanism in Mannich reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1501-1510. doi: 10.11862/CJIC.20240078
15. [15]
  Qin Hu , Liuyun Chen , Xinling Xie , Zuzeng Qin , Hongbing Ji , Tongming Su . Ni掺杂构建电子桥及激活MoS₂惰性基面增强光催化分解水产氢. Acta Physico-Chimica Sinica, 2024, 40(11): 2406024-. doi: 10.3866/PKU.WHXB202406024
16. [16]
  Chengqian Mao , Yanghan Chen , Haotong Bai , Junru Huang , Junpeng Zhuang . Photodimerization of Styrylpyridinium Salt and Its Application in Silk Screen Printing. University Chemistry, 2024, 39(5): 354-362. doi: 10.3866/PKU.DXHX202312014
17. [17]
  Juntao Yan , Liang Wei . 2D S-Scheme Heterojunction Photocatalyst. Acta Physico-Chimica Sinica, 2024, 40(10): 2312024-. doi: 10.3866/PKU.WHXB202312024
18. [18]
  Zhanggui DUAN , Yi PEI , Shanshan ZHENG , Zhaoyang WANG , Yongguang WANG , Junjie WANG , Yang HU , Chunxin LÜ , Wei ZHONG . Preparation of UiO-66-NH₂ supported copper catalyst and its catalytic activity on alcohol oxidation. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 496-506. doi: 10.11862/CJIC.20230317
19. [19]
  Juan WANG , Zhongqiu WANG , Qin SHANG , Guohong WANG , Jinmao LI . NiS and Pt as dual co-catalysts for the enhanced photocatalytic H₂ production activity of BaTiO₃ nanofibers. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1719-1730. doi: 10.11862/CJIC.20240102
20. [20]
  Asif Hassan Raza , Shumail Farhan , Zhixian Yu , Yan Wu . 用于高效制氢的双S型ZnS/ZnO/CdS异质结构光催化剂. Acta Physico-Chimica Sinica, 2024, 40(11): 2406020-. doi: 10.3866/PKU.WHXB202406020

Get Citation

PDF

XML

Metrics

PDF Downloads(10)
Abstract views(706)
HTML views(139)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142