Citation: Bi-Yun SU, Ting-Yu YAN, Xiao-Teng LI, Dan-Dan PAN, Paison FAIDA, Li-Qin DING. Influence of the Substituents on Imino-aryl Ring of Mono(imino)pyrrole-Ni^Ⅱ Complexes to Their Ethylene Polymerization Catalytic Performance[J]. Chinese Journal of Structural Chemistry, ;2020, 39(6): 1093-1102. doi: 10.14102/j.cnki.0254-5861.2011-2548 shu

Influence of the Substituents on Imino-aryl Ring of Mono(imino)pyrrole-Ni^Ⅱ Complexes to Their Ethylene Polymerization Catalytic Performance

a.
College of Chemistry and Chemical Engineering, Xi'an Shiyou University, Xi'an 710065, China
b.
PetroChina Hohhot Petrochemical Company, 010070, China

Corresponding author: Bi-Yun SU, subiyun@xsyu.edu.cn
Received Date: 25 June 2019
Accepted Date: 14 November 2019

Fund Project: the National Natural Science Foundation of China 51674200the Science and Technology Research Program of Shaanxi Province 2019JM-421the Science and Technology Research Program of Shaanxi Province 2018JM2035

Figures(4)

In order to study the influence of substituents on imino-aryl rings of mono(imino)pyrrole-transition metal complexes to their ethylene polymerization performance, a series of mono(imine)pyrroles (L1-L3) were synthesized by microwave irradiation from 2-acetylpyrrole and a series of 2, 6-position disubstituted anilines (substituent: H, Me, Et). A simplified synthetic method was introduced to prepare the corresponding nickel complexes NiL₂ (1~3) with direct condensation of mono(imine)pyrrole ligands and nickel dichloride. All the compounds were fully characterized by ¹H NMR, IR, EA, MS, and X-ray crystal diffraction. Ligand L3 (C₁₆H₂₀N₂, M_r = 240.34) belongs to the triclinic system, space group P\begin{document}$ \overline 1 $\end{document}, with a = 7.9606(19), b = 9.028(2), c = 11.205(3) Å, the final R = 0.0606 and wR = 0.1875. Complex 3 (C₃₂H₃₈N₄Ni, M_r = 537.37) belongs to the monoclinic system, space group C2/c with a = 19.811(3), b = 11.262(2), c = 26.004(4) Å, the final R = 0.0388 and wR = 0.1020. The crystal structures indicated that all the Ni^Ⅱ complexes have similar tetra-coordinated geometries, in which the ligand chelated to the center nickel with a 2:1 molar ratio. Catalytic properties of the Ni^Ⅱ complexes for ethylene polymerization were systematically investigated, and the results showed a regular increase of catalytic activities with steric hindrance of the substituents on the imino-aryl ring of Ni^Ⅱ complexes.
- mono(imino)pyrrole ligand,
- Ni^Ⅱ complex,
- crystal structure,
- ethylene polymerization,
- catalytic performance
1. [1]
  Small, B. L.; Brookhart, M. Iron-based catalysts with exceptionally high activities and selectivities for oligomerization of ethylene to linear α-olefins. J. Am. Chem. Soc. 1998, 120, 7143–7144. doi: 10.1021/ja981317q
2. [2]
  Small, B. L.; Brookhart, M. US Patent, E. I. du Pont de Nemours and Company. 6150482. 2000-11-21.
3. [3]
  Britovsek, G. J. P.; Gibson, V. C.; Kimberley, B. S.; Maddox, P. J.; Mctavish, S. J.; Solan, G. A.; White, A. J. P.; Williams, D. J. Novel 7olefin polymerization catalysts based on iron and cobalt. Chem. Commun. 1998, 7, 849–850.
4. [4]
  Britovsek, G. J. P.; Mastroianni, S.; Solan, G. A.; Baugh, S. P. D.; Redshaw, C.; Gibson, V. C.; White, A. J. P.; Williams, D. J. Oligomerisation of ethylene by bis(imino)pyridyliron and cobalt complexes. Chem. Eur. J. 2000, 6, 2221–2231. doi: 10.1002/1521-3765(20000616)6:12<2221::AID-CHEM2221>3.0.CO;2-U
5. [5]
  Bruin de B.; Bill, E.; Bothe, E. Molecular and electronic structures of bis(pyridine-2, 6-diimine)metal complexes [ML₂](PF₆)_n (n = 0, 1, 2, 3; M = Mn, Fe, Co, Ni, Cu, Zn). Inorg. Chem. 2000, 39, 2936–2947. doi: 10.1021/ic000113j
6. [6]
  Zhang, Z. C.; Chen, S. T.; Zhang, X. F.; Li, H. Y.; Ke, Y. C.; Lu, Y. Y.; Hu, Y. L. A series of novel 2, 6-bis(imino)pyridyl iron catalysts: synthesis, characterization and ethylene oligomerization. J. Mol. Catal. A: Chem. 2005, 230, 1–8. doi: 10.1016/j.molcata.2004.11.028
7. [7]
  Gudasi, K. B.; Patil, S. A.; Vadavi, R. S.; Shenoy, R. V.; Patil, M. S. Synthesis and spectral characterization of some transition metal complexes containing pentadentate SNNNS donor heterocyclic Schiff base ligands. Trans. Met. Chem. 2005, 30, 1014–1019. doi: 10.1007/s11243-005-6297-z
8. [8]
  Gudasi, K. B.; Patil, S. A.; Vadavi, R. S.; Shenoy, R. V.; Nethaji, M.; Bligh, S. W. A. Synthesis and spectral investigation of manganese(Ⅱ), cadmium(Ⅱ) and oxovanadium(IV) complexes with 2, 6-diacetylpyridine bis(2-aminobenzoylhydrazone): crystal structure of manganese(Ⅱ) and cadmium(Ⅱ) complexes. Inorganica Chimica Acta 2006, 359, 3229–3236. doi: 10.1016/j.ica.2006.03.009
9. [9]
  Ionkin, A. S.; Marshall, W. J.; Adelman, D. J.; Barbara, B. F.; Fish, B. M.; Schiffhauer, M. F. High-temperature catalysts for the production of α-olefins based on iron(Ⅱ) and iron(Ⅲ) tridentate bis(imino)pyridine complexes with double pattern of substitution: ortho-methyl plus meta-aryl. Organometallics 2006, 25, 2978–2992. doi: 10.1021/om051069o
10. [10]
  Britovsek, G. J. P.; Gibson, V. C.; Hoarau, O. D.; Spitzmesser, S. K.; White, A. J. P.; Williams, D. J. Iron and cobalt ethylene polymerization catalysts: variations on the central donor. Inorg. Chem. 2003, 42, 3454–3465. doi: 10.1021/ic034040q
11. [11]
  Beaufort, L.; Benvenuti, F.; Noels, A. F. Iron(Ⅱ)-ethylene polymerization catalysts bearing 2, 6-bis(imino)pyrazine ligands: part I. Synthesis and characterization. J. Mol. Catal. A: Chem. 2006, 260, 210–214. doi: 10.1016/j.molcata.2006.07.005
12. [12]
  Dawson, D. M.; Walker, D. A.; Thornton-Pett, M.; Bochmann, M. Synthesis and reactivity of sterically hindered iminopyrrolato complexes of zirconium, iron, cobalt and nickel. J. Chem. Soc., Dalton Trans. 2000, 4, 459–466.
13. [13]
  Gibson, V. C.; Spitzmesser, S. K.; White, A. J. P.; Williams, D. J. Synthesis and reactivity of 1, 8-bis(imino)carbazolide complexes of iron, cobalt and manganese. Dalton Trans. 2003, 13, 2718–2727.
14. [14]
  Nomura, K.; Sidokmai, W.; Imanishi, Y. Ethylene polymerization catalyzed by ruthenium and iron complexes containing 2, 6-bis(2-oxazolin-2-yl)pyridine (pybox) ligand-cocatalyst system. Bull Chem. Soc. Jpn. 2000, 73, 599–605. doi: 10.1246/bcsj.73.599
15. [15]
  Sun, W. H.; Tang, X. B.; Gao, T. L.; Wu, B.; Zhang, W. J.; Ma, H. W. Synthesis, characterization, and ethylene oligomerization and polymerization of ferrous and cobaltous 2-(ethylcarboxylato)-6-iminopyridyl complexes. Organometallics 2004, 23, 5037–5047. doi: 10.1021/om0496636
16. [16]
  Tang, X. B.; Sun, W. H.; Gao, T. L.; Hou, J. X.; Chen, J. T.; Chen, W. Nickel(Ⅱ) complexes bearing 2-ethylcarboxylate-6-iminopyridyl ligands: synthesis, structures and their catalytic behavior for ethylene oligomerization and polymerization. J. Organomet. Chem. 2005, 690, 1570–1580. doi: 10.1016/j.jorganchem.2004.12.027
17. [17]
  Su, B. Y.; Zhao, J. S.; Gao, Q. C. Crystal structure and ethylene oligomerization catalytic activity of {2-carbethoxy-6-[1-[(2, 6-diethyl-phenyl)imino]ethyl]pyridine}CoCl₂. Chin. J. Chem. 2007, 25, 121–124. doi: 10.1002/cjoc.200790005
18. [18]
  Su, B. Y.; Zhao, J. S. Structure and ethylene polymerization/oligomerization behavior of 2-carbethoxy-6-iminopyridine-based transition metal complexes. Polyhedron 2006, 25, 3289–3298. doi: 10.1016/j.poly.2006.06.015
19. [19]
  Su, B. Y.; Feng, G. X. Influence of metal centers of 2, 6-bis(imino)pyridyl transition metal complexes on ethylene polymerization/oligomerization catalytic activities. Poly. Inter. 2010, 59, 1058–1062.
20. [20]
  Su, B. Y.; Zhao, J. S.; Zhang, Q. Z.; Qing, W. L. Cobalt(Ⅱ) and nickel(Ⅱ) complexes bearing mono(imino)pyridyl and bis(imino)pyridyl ligands: preparation, structure and ethylene polymerization/oligomerization behaviors. Poly. Inter. 2009, 58, 1051–1057. doi: 10.1002/pi.2631
21. [21]
  Anderson, C. E.; Batsanov, A. S.; Dyer, P. W.; Fawcett, J.; Howard, J. A. K. Chelating N-pyrrolylphosphino-N΄-arylaldimine ligands: synthesis, ligand behaviour and applications in catalysis. Dalton Trans. 2006, 45, 5362–5378.
22. [22]
  Carabineiro, S. A.; Silva, L. C.; Gomes, P. T.; Pereira, L. C. J.; Veiros, L. F.; Pascu, S. I.; Duarte, M. T.; Namorado, S.; Henriques, R. T. Synthesis and characterization of tetrahedral and square planar bis(iminopyrrolyl) complexes of cobalt(Ⅱ). Inorg. Chem. 2007, 46, 6880–6890. doi: 10.1021/ic062125w
23. [23]
  Imhof, W. Bis{2-[(phenylimino)methyl]-1H-pyrrol-1-ido}palladium(Ⅱ). Acta Cryst. 2012, E68, m1567.
24. [24]
  Imhof, W. Bis{2-[(2, 4, 6-trimethylphenyl)iminomethyl]pyrrol-1-idopalladium(Ⅱ). Acta Cryst. 2013, E69, m96.
25. [25]
  Pe΄rez-Puente, P.; Jesu΄s de E.; Flores, J. C.; Go΄mez-Sal, P. Synthesis of 2-(N-arylimino-κN-methyl)pyrrolide-κN complexes of nickel. J. Organomet. Chem. 2008, 693, 3902–3906. doi: 10.1016/j.jorganchem.2008.09.067
26. [26]
  Su, B. Y.; Li, X. T.; Wang, X. D.; Li, Q. D. Efficient microwave-assisted syntheses of a series of novel mono(imino)pyrrolyl compounds. Heterocycles 2015, 91, 1955–1963. doi: 10.3987/COM-15-13265
27. [27]
  David, M. D.; Dennis, A. W.; Mark, T.; Manfred, B. Synthesis and reactivity of sterically hindered iminopyrrolato complexes of zirconium, iron, cobalt and nickel. J. Chem. Soc., Dalton Trans. 2000, 41, 459–466.
28. [28]
  Gibson, V. C.; Maddox, P. J.; Newton, C.; Redshaw, C.; Solan, G. A.; White, A. J. P.; Williams, D. J. Chromium(Ⅲ) complexes bearing N, N-chelate ligands as ethene polymerization catalysts. Chem. Commun. 1998, 16, 1651–1652.
29. [29]
  Song, S. J.; Zhao, W. Z.; Wang, L.; Redshawb, C.; Wang, F. S.; Sun, W. H. Synthesis, characterization and catalytic behavior toward ethylene of cobalt(Ⅱ) and iron(Ⅱ) complexes bearing 2-(1-aryliminoethylidene)quinolines. J. Organomet. Chem. 2011, 696, 3029–3035. doi: 10.1016/j.jorganchem.2011.06.003
30. [30]
  Song, S. J.; Xiao, T. P. F.; Redshaw, C.; Hao, X.; Wang, F. S.; Sun, W. H. Iron(Ⅱ) and cobalt(Ⅱ) complexes bearing 8-(1-aryliminoethylidene) quinaldines: synthesis, characterization and ethylene dimerization behavior. J. Organomet. Chem. 2011, 696, 2594–2599. doi: 10.1016/j.jorganchem.2011.03.039
31. [31]
  Sun, W. H.; Hao, P.; Zhang, S.; Shi, Q.; Zuo, W.; Tang, X.; Lu, X. Iron(Ⅱ) and cobalt(Ⅱ) 2-(benzimidazolyl)-6-(1-(arylimino)ethyl)pyridyl complexes as catalysts for ethylene oligomerization and polymerization. Organometallics 2007, 26, 2720–2734. doi: 10.1021/om0700819
32. [32]
  Xiao, L.; Gao, R.; Zhang, M.; Li, Y.; Cao, X.; Sun, W. H. 2-(1H-2-Benzimidazolyl)-6-(1-(arylimino)ethyl)pyridyl iron(Ⅱ) and cobalt(Ⅱ) dichlorides: syntheses, characterizations, and catalytic behaviors toward ethylene reactivity. Organometallics 2009, 28, 2225–2233. doi: 10.1021/om801141n
33. [33]
  Su, B. Y.; Wang, J. X.; Liu, X.; Li, Q. D. Bis(2-{1-[(2, 4, 6-trimethylphenyl)imino]ethylpyrrol-1-ido-κ(2)N, N') nickel(Ⅱ): a supramolecular structure formed by C–H. π(arene) hydrogen bonds. Acta Cryst. 2013, C69, 851–854.
34. [34]
  Su, B. Y.; Wang, X. D.; Wang, J. X.; Li, X. T. Nickel(Ⅱ) complexes with mono(imino) pyrrole ligands: preparation, structure and ethylene polymerization behavior. J. Coord. Chem. 2015, 68, 4212–4223. doi: 10.1080/00958972.2015.1103371
35. [35]
  Sheldrick, G. M. SHELXL-97, Program for Refinement of Crystal Structures. University of Göttingen: Germany 1997.
36. [36]
  Su, B. Y.; Li, L.; Wang, J. X.; Li, X. Y. N-[1-(1H-pyrrol-2-yl)ethylidene]aniline. Acta Cryst. 2012, E68, o2888
37. [37]
  Atiqullah, M.; Hammawa, H.; Hamid, H. Modeling the solubility of ethylene and propylene in a typical polymerization diluent: some selected situations. Eur. Polym. J. 1998, 34, 1511–1520. doi: 10.1016/S0014-3057(98)00005-6
38. [38]
  Fogg, P. G. T.; Gerrard, W. Solubility of Gasesin Liquids. Wiley, Chichester 1991.
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Influence of the Substituents on Imino-aryl Ring of Mono(imino)pyrrole-NiⅡ Complexes to Their Ethylene Polymerization Catalytic Performance

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通讯作者: 陈斌, bchen63@163.com

Influence of the Substituents on Imino-aryl Ring of Mono(imino)pyrrole-Ni^Ⅱ Complexes to Their Ethylene Polymerization Catalytic Performance