Citation: Li-Ping GUO, Ren-Yuan SONG. Rare-earth Metal Dialkyl Complexes Supported by 1, 3-Disubstituted Indolyl Ligand: Synthesis, Characterization and Catalytic Activity for Isoprene Polymerization[J]. Chinese Journal of Structural Chemistry, ;2021, 40(8): 1055-1060. doi: 10.14102/j.cnki.0254–5861.2011–3172 shu

Rare-earth Metal Dialkyl Complexes Supported by 1, 3-Disubstituted Indolyl Ligand: Synthesis, Characterization and Catalytic Activity for Isoprene Polymerization

Li-Ping GUO ^{a, b,,} ,
Ren-Yuan SONG ^a

a.
Anhui Provincial Engineering Laboratory of Silicon-based Materials, Bengbu University, Bengbu 233030, China
b.
The Key Laboratory of Functional Molecular Solids, Ministry of Education, Anhui Normal University, Wuhu 241000, China

Corresponding author: Li-Ping GUO, guoliping251@126.com
Received Date: 10 March 2021
Accepted Date: 16 April 2021

Fund Project: the Natural Science Foundation of Anhui Province 2008085ME174financial support from Anhui Normal University FMS201915

Figures(3)

Rare-earth metal dialkyl complexes [1-Bn-3-(DippN=CH)C₈H₄N]RE(CH₂SiMe₃)₂(thf)₂ (Dipp = 2, 6-ⁱPr₂C₆H₃, RE = Y (1) and Er (2)) were prepared through the cyclometalation reactions of the N-Bn-3-imino-functionalized indolyl ligand 1-Bn-3-(DippN=CH)C₈H₅N with one equivalent of rare-earth metal trialkyl precursors. The structures of compounds 1 and 2 were confirmed by X-ray crystal analyses and characterized by elemental analysis, IR, NMR spectroscopy wherein applicable. In the presence of cocatalysts, these rare-earth metal dialkyl complexes initiated isoprene polymerization with a high activity (95% conversion of 2000 equivalent of isoprene in 360 min), producing polymers with high regioselectivity (1, 4-polymers up to 91%).
- indolyl ligand,
- rare-earth metal dialkyl complex,
- isoprene,
- polymerization
1. [1]
  Nishiura, M.; Hou, Z. M. Novel polymerization catalysts and hydride clusters from rare-earth dialkyls. Nat. Chem. 2010, 2, 257–268. doi: 10.1038/nchem.595
2. [2]
  Cheng, J. H.; Hou, Z. M. Rare-earth dialkyl and dihydride complexes bearing monoanionic ancillary ligands. Sci. China Chem. 2011, 54, 2032–2037. doi: 10.1007/s11426-011-4439-z
3. [3]
  Arndt, S.; Okuda, J. Mono(cyclopentadienyl) complexes of the rare-earths. Chem. Rev. 2002, 102, 1953–1976. doi: 10.1021/cr010313s
4. [4]
  Mao, W. Q.; Chen, Y. F. Rare-earth metal complexes of β-diketiminato ligands bearing pendant nitrogen or oxygen donors. Coord. Chem. Rev. 2017, 346, 77–90. doi: 10.1016/j.ccr.2016.12.007
5. [5]
  (a) Cheng, J. H.; Saliu, K.; Kiel, G. Y.; Ferguson, M. J.; McDonald, R.; Takats, J. Scorpionate-supported dialkyl and dihydride lanthanide complexes: ligand- and solvent-dependent cluster hydride formation. Angew. Chem. Int. Ed. 2008, 4910–4913.
  (b) Yi, W. Y.; Zhang, J.; Zhang, F. J.; Zhang, Y.; Chen, Z. X.; Zhou, X. G. Versatile reactivity of scorpionate-anchored yttrium-dialkyl complexes towards unsaturated substrates. Eur. J. Chem. 2013, 19, 11975–11983.
6. [6]
  (a) Yu, X. Y.; Li, M.; Hong, J. Q.; Zhou, X. G.; Zhang, L. X. Living 3, 4-(co)polymerization of isoprene/myrcene and one-pot synthesis of a polyisoprene blend catalyzed by binuclear rare-earth metal amidinate complexes. Chem. Eur. J. 2019, 25, 2569–2576.
  (b) Rad'kova, N. Y.; Tolpygin, A. O.; Rad'kov, V. Y.; Khamaletdinova, N. M.; Cherkasov, A. V.; Fukin, G. K.; Trifonov, A. A. Bis(alkyl) rare-earth complexes coordinated by bulky tridentate amidinate ligands bearing pendant Ph₂P=O and Ph₂P=NR groups. Synthesis, structures and catalytic activity in stereospecific isoprene polymerization. Dalton Trans. 2016, 45, 18572–18584.
7. [7]
  (a) Zhu, X.; Zhou, S.; Wang, S.; Wei, Y.; Zhang, L.; Wang, F.; Wang, S. Y.; Feng, Z. Rare-earth metal complexes having an unusual indolyl-1, 2-dianion through C–H activation with a novel η¹: (μ₂-η¹: η¹) bonding with metals. Chem. Commun. 2012, 48, 12020–12022.
  (b) Feng, Z.; Zhu, X.; Wang, S.; Wang, S. Y.; Zhou, S.; Wei, Y.; Zhang, G.; Deng, B.; Mu, X. Synthesis, structure and reactivity of lanthanide complexes incorporating indolyl ligands in novel hapticities. Inorg. Chem. 2013, 52, 9549–9556.
  (c) Zhu, X.; Wang, S.; Zhou, S.; Wei, Y.; Zhang, L.; Wang, F.; Feng, Z.; Guo, L.; Mu, X. Lanthanide amido complexes incorporating amino-coordinate lithium bridged bis(indolyl) ligands: synthesis, characterization, and catalysis for hydrophosphonylation of aldehydes and aldimines. Inorg. Chem. 2012, 51, 7134–7143.
  (d) Zhang, G.; Wei, Y.; Guo, L.; Zhu, X.; Wang, S.; Zhou, S.; Mu, X. Dinuclear rare-earth metal alkyl complexes supported by indolyl ligands in μ-η²: η¹: η¹ hapticities and their high catalytic activity for isoprene 1, 4-cis-polymerization. Chem. Eur. J. 2015, 21, 2519–2526.
  (e) Yu, L.; Wang, F. H.; Wang, H.; Wang, S. Y.; Wu, Y. J.; Gu, X. X. Synthesis, structure and catalytic activity of rare-earth metal amino complexes incorporating imino-functionalized indolyl ligand. J. Organo. Chem. 2021, 934, 121661.
  (f) Hong, D. J.; Zhu, X. C.; Wang, S. W.; Wei, Y.; Zhou, S. L.; Huang, Z. M.; Zhu, S.; Wang, R. R.; Yue, W. R.; Mu, X. L. Synthesis, characterization, and reactivity of dinuclear organo-rare-earth metal alkyl complexes supported by 2-amidate functionalized indolyl ligands: substituent effects on coordination and reactivity. Dalton Trans. 2019, 48, 5230–5242.
  (g) Wei, Y.; Song, L. L.; Jiang, L.; Huang, Z. M.; Wang, S. W.; Yuan, Q. B.; Mu, X. L.; Zhu, X. C.; Zhou, S. L. Aluminum complexes with Schiff base bridged bis(indolyl) ligands: synthesis, structure, and catalytic activity for polymerization of rac-lactide. Dalton Trans. 2019, 48, 15290–15299.
  (h) Feng, Z. J.; Huang, Z. M.; Wang, S. W.; Wei, Y.; Zhou, S. L.; Zhu, X. C. Synthesis and characterization of 2-t-butylimino-functionalized indolyl rare-earth metal amido complexes for the catalytic addition of terminal alkynes to carbodiimides: the dimeric complexes with the alkynide species in the μ-η¹: η² bonding modes. Dalton Trans. 2019, 48, 11094–11102.
8. [8]
  (a) Guo, L. P.; Zhu, X. C.; Zhang, G. C.; Wei, Y.; Ning, L. X.; Zhou, S. L.; Feng, Z. J.; Wang, S. W.; Mu, X. L.; Chen, J.; Jiang, Y. Z. Synthesis and characterization of organo-rare-earth metal monoalkyl complexes supported by carbon σ-bonded indolyl ligands: high specific isoprene 1, 4-cis polymerization catalysts. Inorg. Chem. 2015, 54, 5725–5731.
  (b) Guo, L. P.; Wang, S. W.; Wei, Y.; Zhou, S. L.; Zhu, X. C.; Mu, X. L. Reactivity of 1, 3-disubstituted indoles with lithium compounds: substituents and solvents effects on coordination and reactivity of resulting 1, 3-disubstituted-2-indolyl lithium complexes. Inorg. Chem. 2017, 56, 6197–6207.
9. [9]
  (a) Wenkert, E.; Udelhofen, J. H.; Bhattacharyya, N. K. 3-Hydroxymethyleneoxindole and its derivatives. J. Am. Chem. Soc. 1959, 81, 3763–3768.
  (b) Zheng, C.; Lu, Y.; Zhang. J.; Chen, X.; Chai, Z.; Ma, W.; Zhao, G. The enantioselective, organocatalyzed Diels-Alder reaction of 2-vinylindoles with α, β-unsaturated aldehydes: an efficient route to functionalized tetrahydrocarbazoles. Chem. Eur. J. 2010, 16, 5853–5857.
  (c) Kalir, A.; Szara, S. Synthesis of 1-benzyltryptamine. J. Med. Chem. 1966, 9, 793–794.
10. [10]
  Sheldrick, G. M. SADABS: Program for Empirical Absorption Correction of Area Detector Data. University of Göttingen, Germany 1996.
11. [11]
  Sheldrick, G. M. SHELXTL 5.10 for Windows NT: Structure Determination Software Programs, Bruker Analytical X-ray Systems, Inc., Madison, WI 1997.
12. [12]
  Wang, D.; Cui, D. M.; Miao, W.; Li, S. H.; Huang, B. T. Rare earth metal complexes bearing thiophene amido ligand: synthesis and structural characterization. Dalton Trans. 2007, 4576–4581.
13. [13]
  Luconi, L.; Lyubov, D. M.; Bianchini, C.; Rossin, A.; Faggi, C.; Fukin, G. K.; Cherkasov, A. V.; Shavyrin, A. S.; Trifonov, A. A.; Giambastiani, G. Yttrium-amidopyridinate complexes: synthesis and characterization of yttrium-alkyl and yttrium-hydrido derivatives. Eur. J. Inorg. Chem. 2010, 608–620.
14. [14]
  Shannon, R. D. Revised effective ionic radii and systematic studied of interatomic distances in halides and chalcogenides. Acta Cryst. 1976, A32, 751–767.
15. [15]
  Hayes, P.; Piers, W.; Parvez, M. Cationic organoscandium β-dikediminato chemistry: arene exchange kinetics in solvent separated ion pairs. J. Am. Chem. Soc. 2003, 125, 5622–5623. doi: 10.1021/ja034680s
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