Synthesis of binuclear phenoxyimino organoaluminum complexes and their use as the catalyst precursors for efficient ring-opening polymerisation of ε-caprolactone
Abstract
A series of novel binuclear phenoxyimino organoaluminum complexes of the type [(RN=CH)C6H3OAlMe2]2 [R = C6H5 (2a), 2,6-(i)Pr2C6H3 (2b), 2,6-Ph2C6H3 (2c), adamantyl (2d), (t)Bu (2e)] have been prepared in high yields, and these complexes were identified by (1)H, (13)C NMR and elemental analysis. Structural analysis for 2a-e revealed that these complexes have a distorted tetrahedral geometry around Al and both the Al-O and the Al-N bond distances were considerably influenced by substituents in the imino groups. The complexes were tested as catalyst precursors for ring-opening polymerisation (ROP) of ε-caprolactone (CL) in the presence of BnOH, and their catalytic activities were strongly affected by the catalyst structures and polymerisation conditions. An efficient living ROP has been achieved using the 2b/BnOH system.
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syn-Al complex (complex 9) was more stable with a tolerance for alcohol than anti-Al complex (complex 10) through the 1H NMR spectra of complex 9 and complex 10 with 10 equiv. BnOH.
“In addition, syn-Al complex (complex 9) was more stable with a tolerance for alcohol than anti-Al complex (complex 10) through the 1 H NMR spectra of complex 9 and complex 10 with 10 equiv.BnOH, respectively.”
From Multinuclear metal catalysts in ring-opening polymerization of ε‑caprolactone and lactide: Cooperative and electronic effects between metal centers (2023) · cites this paper as [74]
The molar mass distributions of producing PLAs catalyzed by syn-Al complex (complex 9) remained unimodal and narrow, suggesting an immortal polymerization.
“and the molar mass distributions of producing PLAs catalyzed by syn-Al complex (complex 9) remained unimodal and narrow, suggesting an immortal polymerization.”
From Multinuclear metal catalysts in ring-opening polymerization of ε‑caprolactone and lactide: Cooperative and electronic effects between metal centers (2023) · cites this paper as [74]
The syn-Al complex (complex 9) exhibited higher catalytic activity in rac-LA polymerization compared with the anti-Al complex (complex 10).
“The results revealed that the syn-Al complex (complex 9) exhibited higher catalytic activity in rac-LA polymerization compared with the anti-Al complex (complex 10)”
From Multinuclear metal catalysts in ring-opening polymerization of ε‑caprolactone and lactide: Cooperative and electronic effects between metal centers (2023) · cites this paper as [74]
The higher catalytic activity of syn-Al complex 9 may be attributable to the cooperative effect of two neighbouring Al centers (Al-Al distance of complex 9 was 6.665 Å).
“This may be attributable to the cooperative effect of two neighbouring Al centers (Al-Al distance of complex 9 was 6.665 Å).”
From Multinuclear metal catalysts in ring-opening polymerization of ε‑caprolactone and lactide: Cooperative and electronic effects between metal centers (2023) · cites this paper as [74]
Cites
Polymeric systems for controlled drug release
Uhrich, K. E., Cannizzaro, S. M., Langer, R. S., & Shakesheff, K. M. (1999) · Chemical Reviews · doi:10.1021/cr940351u · Cited by 2,633 · see citing works
Controlled Ring-Opening Polymerization of Lactide and Glycolide
Dechy-Cabaret, O., Martin-Vaca, B., & Bourissou, D. (2004) · Chemical Reviews · doi:10.1021/cr040002s · Cited by 2,257 · see citing works
Chemical syntheses of biodegradable polymers
Okada, M. (2002) · Progress in Polymer Science · doi:10.1016/s0079-6700(01)00039-9 · Cited by 1,202 · see citing works
WU, J., YU, T., CHEN, C., & LIN, C. (2006) · Coordination Chemistry Reviews · doi:10.1016/j.ccr.2005.07.010 · Cited by 779 · see citing works
Ovitt, T. M., & Coates, G. W. (2002) · Journal of the American Chemical Society · doi:10.1021/ja012052+ · Cited by 713 · see citing works
Spassky, N., Wisniewski, M., Pluta, C., & Le Borgne, A. (1996) · Macromolecular Chemistry and Physics · doi:10.1002/macp.1996.021970902 · Cited by 627 · see citing works
Multinuclear Olefin Polymerization Catalysts
Delferro, M., & Marks, T. J. (2011) · Chemical Reviews · doi:10.1021/cr1003634 · Cited by 619 · see citing works
Controlled and Stereoselective Polymerization of Lactide: Kinetics, Selectivity, and Microstructures
Zhong, Z., Dijkstra, P. J., & Feijén, J. (2003) · Journal of the American Chemical Society · doi:10.1021/ja0347585 · Cited by 503 · see citing works
Ovitt, T. M., & Coates, G. W. (1999) · Journal of the American Chemical Society · doi:10.1021/ja990088k · Cited by 502 · see citing works
Nomura, N., Ishii, R., Akakura, M., & Aoi, K. (2002) · Journal of the American Chemical Society · doi:10.1021/ja0175789 · Cited by 478 · see citing works
Radano, C. P., Baker, G. L., & Smith, M. R. (2000) · Journal of the American Chemical Society · doi:10.1021/ja9930519 · Cited by 403 · see citing works
Stereoselective Polymerization of rac-Lactide Using a Monoethylaluminum Schiff Base Complex
Tang, Z., Chen, X., Pang, X., Yang, Y., Zhang, X., & Jing, X. (2004) · Biomacromolecules · doi:10.1021/bm034467o · Cited by 215 · see citing works
Liu, Y., Ko, B., & Lin, C. (2001) · Macromolecules · doi:10.1021/ma0104579 · Cited by 204 · see citing works
Self-citationDu, H., Pang, X., Yu, H., Zhuang, X., Chen, X., Cui, D., Wang, X., & Jing, X. (2007) · Macromolecules · doi:10.1021/ma062194u · Cited by 184 · see citing works
Chen, H., Dutta, S., Huang, P.-Y., & Lin, C. (2012) · Organometallics · doi:10.1021/om201281w · Cited by 170 · see citing works
Wisniewski, M., Borgne, A. L., & Spassky, N. (1997) · Macromolecular Chemistry and Physics · doi:10.1002/macp.1997.021980424 · Cited by 162 · see citing works
Nomura, N., Aoyama, T., Ishii, R., & Kondo, T. (2005) · Macromolecules · doi:10.1021/ma050606d · Cited by 140 · see citing works
Polymerization of Lactide Using Achiral Bis(pyrrolidene) Schiff Base Aluminum Complexes
Du, H., Velders, A. H., Dijkstra, P. J., Zhong, Z., Chen, X., & Feijén, J. (2009) · Macromolecules · doi:10.1021/ma802564s · Cited by 136 · see citing works
Ko, B., & Lin, C. (1999) · Macromolecules · doi:10.1021/ma991055s · Cited by 134 · see citing works
Hu, T., Tang, L., Li, X., Li, Y., & Hu, N. (2005) · Organometallics · doi:10.1021/om049223e · Cited by 131 · see citing works
Self-citationPang, X., Du, H., Chen, X., Wang, X., & Jing, X. (2008) · Chemistry - A European Journal · doi:10.1002/chem.200701473 · Cited by 129 · see citing works
Wang, Y., & Ma, H. (2012) · Chemical Communications · doi:10.1039/c2cc31716h · Cited by 127 · see citing works
Gong, S., & Ma, H. (2008) · Dalton Transactions · doi:10.1039/b802638f · Cited by 126 · see citing works
Arbaoui, A., Redshaw, C., & Hughes, D. L. (2008) · Chemical Communications · doi:10.1039/b810417d · Cited by 122 · see citing works
Iwasa, N., Katao, S., Liu, J.-Y., Fujiki, M., Furukawa, Y., & Nomura, K. (2009) · Organometallics · doi:10.1021/om8011882 · Cited by 114 · see citing works
Self-citationHydrogen-bond supramolecular structure of group 13 Schiff base complexes
Lewiński, J., Zachara, J., Justyniak, I., & Dranka, M. (2004) · Coordination Chemistry Reviews · doi:10.1016/j.ccr.2004.11.013 · Cited by 112 · see citing works
Ring-Opening Polymerization of ε-Caprolactone and l -Lactide Using Aluminum Thiolates as Initiator
Huang, C., Wang, F.-C., Ko, B., Yu, T., & Lin, C. (2001) · Macromolecules · doi:10.1021/ma0014719 · Cited by 111 · see citing works
Yao, W., Mu, Y., Gao, A., Gao, W., & Ye, L. (2008) · Dalton Transactions · doi:10.1039/b719017d · Cited by 107 · see citing works
Lewiński, J., Horeglad, P., Dranka, M., & Justyniak, I. (2004) · Inorganic Chemistry · doi:10.1021/ic049337i · Cited by 102 · see citing works
Hsueh, M., Huang, B., & Lin, C. (2002) · Macromolecules · doi:10.1021/ma020574j · Cited by 99 · see citing works
Iwasa, N., Fujiki, M., & Nomura, K. (2008) · Journal of Molecular Catalysis A Chemical · doi:10.1016/j.molcata.2008.06.009 · Cited by 95 · see citing works
Self-citationHaddad, M., Laghzaoui, M., Welter, R., & Dagorne, S. (2009) · Organometallics · doi:10.1021/om9003362 · Cited by 93 · see citing works
Liu, J.-Y., Iwasa, N., & Nomura, K. (2008) · Dalton Transactions · doi:10.1039/b801561a · Cited by 87 · see citing works
Self-citationBhaw‐Luximon, A., Jhurry, D., & Spassky, N. (2000) · Polymer Bulletin · doi:10.1007/s002890050570 · Cited by 84 · see citing works
Gamer, M. T., Roesky, P. W., Palard, I., Hellaye, M. L., & Guillaume, S. M. (2007) · Organometallics · doi:10.1021/om0608307 · Cited by 81 · see citing works
Shen, M., Zhang, W., Nomura, K., & Sun, W. (2009) · Dalton Transactions · doi:10.1039/b910155a · Cited by 74 · see citing works
Self-citationLiu, X., Gao, W., Mu, Y., Li, G., Ye, L., Xia, H., Ren, Y., & Feng, S. (2005) · Organometallics · doi:10.1021/om049143a · Cited by 70 · see citing works
Bouyahyi, M., Roisnel, T., & Carpentier, J. (2011) · Organometallics · doi:10.1021/om200907x · Cited by 70 · see citing works
Sun, W., Shen, M., Zhang, W., Huang, W., Liu, S., & Redshaw, C. (2011) · Dalton Transactions · doi:10.1039/c0dt01207f · Cited by 65 · see citing works
Iwasa, N., Liu, J.-Y., & Nomura, K. (2007) · Catalysis Communications · doi:10.1016/j.catcom.2007.10.025 · Cited by 63 · see citing works
Self-citationShen, M., Huang, W., Zhang, W., Hao, X., Sun, W., & Redshaw, C. (2010) · Dalton Transactions · doi:10.1039/c0dt00514b · Cited by 59 · see citing works
Akatsuka, M., Aida, T., & Inoue, S. (1995) · Macromolecules · doi:10.1021/ma00108a075 · Cited by 57 · see citing works
Structure Investigations of Group 13 Derivatives of N-Phenylsalicylideneimine
Lewiński, J., Zachara, J., Starowieyski, K. B., Ochal, Z., Justyniak, I., Kopeć, T., Stolarzewicz, P., & Dranka, M. (2003) · Organometallics · doi:10.1021/om030331v · Cited by 53 · see citing works
Zhang, W., Wang, Y., Cao, J., Wang, L., Pan, Y., Redshaw, C., & Sun, W. (2011) · Organometallics · doi:10.1021/om2008343 · Cited by 45 · see citing works
Synthesis and catalytic application of aluminium anilido-pyrazolate complexes
Peng, K., & Chen, C. (2009) · Dalton Transactions · doi:10.1039/b905394h · Cited by 45 · see citing works
Isoda, M., Sugimoto, H., Aida, T., & Inoue, S. (1997) · Macromolecules · doi:10.1021/ma961265u · Cited by 35 · see citing works
Web Site: The Gallery of Sweet Rendezvous
Gabius, H., & Rüdiger, H. E. F. (2002) · Angewandte Chemie International Edition · doi:10.1002/1521-3773(20021202)41:23
Flagged first, then by citations
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Wei, Y., Wang, S., & Zhou, S. (2016) · Dalton Transactions · doi:10.1039/c5dt04240b · Cited by 122 · see citing works
Santoro, O., Zhang, X., & Redshaw, C. (2020) · Catalysts · doi:10.3390/catal10070800 · Cited by 111 · see citing works
Wu, L.-J., Lee, W., Kumar Ganta, P., Chang, Y.-L., Chang, Y.-C., & Chen, H.-Y. (2023) · Coordination Chemistry Reviews · doi:10.1016/j.ccr.2022.214847 · Cited by 96 · see citing works
Chen, L., Li, W., Yuan, D., Zhang, Y., Shen, Q., & Yao, Y. (2015) · Inorganic Chemistry · doi:10.1021/acs.inorgchem.5b00022 · Cited by 83 · see citing works
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Röckl, J. L., Schollmeyer, D., Franke, R., & Waldvogel, S. R. (2019) · Angewandte Chemie International Edition · doi:10.1002/anie.201910077 · Cited by 82 · see citing works
Isnard, F., Lamberti, M., Lettieri, L., D'auria, I., Press, K., Troiano, R., & Mazzeo, M. (2016) · Dalton Transactions · doi:10.1039/c6dt02592g · Cited by 72 · see citing works
Strianese, M., Pappalardo, D., Mazzeo, M., Lamberti, M., & Pellecchia, C. (2020) · Dalton Transactions · doi:10.1039/d0dt02639e · Cited by 68 · see citing works
Kan, C., Ge, J., & Ma, H. (2016) · Dalton Transactions · doi:10.1039/c5dt04633e · Cited by 67 · see citing works
Yolsal, U., Shaw, P. J., Lowy, P. A., Chambenahalli, R., & Garden, J. A. (2024) · ACS Catalysis · doi:10.1021/acscatal.3c05103 · Cited by 64 · see citing works
Chang, M.-C., Lu, W.-Y., Chang, H.-Y., Lai, Y.-C., Chiang, M. Y., Chen, H.-Y., & Chen, H.-Y. (2015) · Inorganic Chemistry · doi:10.1021/acs.inorgchem.5b01858 · Cited by 61 · see citing works
Electrosynthesis 2.0 in 1,1,1,3,3,3‐Hexafluoroisopropanol/Amine Mixtures
Röckl, J. L., Dörr, M., & Waldvogel, S. R. (2020) · ChemElectroChem · doi:10.1002/celc.202000761 · Cited by 58 · see citing works
Mandal, M., Chakraborty, D., & Ramkumar, V. (2015) · RSC Advances · doi:10.1039/c4ra17201a · Cited by 52 · see citing works
Isnard, F., Carratù, M., Lamberti, M., Venditto, V., & Mazzeo, M. (2018) · Catalysis Science & Technology · doi:10.1039/c8cy01174e · Cited by 49 · see citing works
Liu, S., Invergo, A. M., McInnis, J. P., Mouat, A. R., Motta, A., Lohr, T. L., Delferro, M., & Marks, T. J. (2017) · Organometallics · doi:10.1021/acs.organomet.7b00641 · Cited by 40 · see citing works
Shi, T., Zheng, Q.-D., Zuo, W.-W., Liu, S.-F., & Li, Z.-B. (2018) · Chinese Journal of Polymer Science · doi:10.1007/s10118-018-2039-5 · Cited by 39 · see citing works
Wang, X., Zhao, K., Al‐Khafaji, Y., Mo, S., Prior, T. J., Elsegood, M. R. J., & Redshaw, C. (2017) · European Journal of Inorganic Chemistry · doi:10.1002/ejic.201601415 · Cited by 38 · see citing works
Luo, W., Shi, T., Liu, S., Zuo, W., & Li, Z. (2017) · Organometallics · doi:10.1021/acs.organomet.7b00106 · Cited by 37 · see citing works
Wang, X., Li, Y., Mu, H., Pan, L., & Li, Y. (2014) · Polymer Chemistry · doi:10.1039/c4py01350f · Cited by 36 · see citing works
Self-citationLee, C.-L., Lin, Y., Jiang, M.-T., Lu, W., Vandavasi, J. K., Wang, L., Lai, Y., Chiang, M. Y.-N., & Chen, H. (2017) · Organometallics · doi:10.1021/acs.organomet.7b00068 · Cited by 36 · see citing works
Osten, K. M., Aluthge, D. C., Patrick, B. O., & Mehrkhodavandi, P. (2014) · Inorganic Chemistry · doi:10.1021/ic501529f · Cited by 35 · see citing works
Liu, J., & Ma, H. (2014) · Dalton Transactions · doi:10.1039/c4dt00353e · Cited by 31 · see citing works
Self-citationMandal, M., Ramkumar, V., & Chakraborty, D. (2019) · Polymer Chemistry · doi:10.1039/c8py01750f · Cited by 31 · see citing works
Kosuru, S. R., Sun, T.-H., Wang, L.-F., Vandavasi, J. K., Lu, W.-Y., Lai, Y.-C., Hsu, S. C. N., Chiang, M. Y., & Chen, H.-Y. (2017) · Inorganic Chemistry · doi:10.1021/acs.inorgchem.7b00763 · Cited by 26 · see citing works
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Nakata, N., Saito, Y., & Ishii, A. (2014) · Organometallics · doi:10.1021/om5001698 · Cited by 22 · see citing works
Hsu, C.-Y., Tseng, H.-C., Vandavasi, J. K., Lu, W.-Y., Wang, L.-F., Chiang, M. Y., Lai, Y.-C., Chen, H.-Y., & Chen, H.-Y. (2017) · RSC Advances · doi:10.1039/c7ra02136d · Cited by 20 · see citing works
Huang, T.-W., Su, R.-R., Lin, Y.-C., Lai, H.-Y., Yang, C.-Y., Senadi, G. C., Lai, Y.-C., Chiang, M. Y.-N., & Chen, H. (2018) · Dalton Transactions · doi:10.1039/c8dt03285h · Cited by 20 · see citing works
Roymuhury, S. K., Mandal, M., Chakraborty, D., & Ramkumar, V. (2021) · Polymer Chemistry · doi:10.1039/d1py00237f · Cited by 20 · see citing works
Liu, J., & Ma, H. (2014) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.27359 · Cited by 16 · see citing works
Self-citationZhang, J., Liu, S., Zuo, W., Ye, H., & Li, Z. (2017) · New Journal of Chemistry · doi:10.1039/c6nj03818b · Cited by 15 · see citing works
Oishi, M., Ichinose, Y., Iwata, N., & Nomura, N. (2019) · Organometallics · doi:10.1021/acs.organomet.9b00540 · Cited by 15 · see citing works
Chang, C., Lee, W., Liou, Y.-C., Chang, Y., Lai, Y., Ding, S., Chen, H., Chen, H., & Chang, Y. (2022) · European Polymer Journal · doi:10.1016/j.eurpolymj.2022.111651 · Cited by 10 · see citing works
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Zhang, D., Pang, W., & Chen, C. (2017) · Journal of Organometallic Chemistry · doi:10.1016/j.jorganchem.2017.03.007 · Cited by 7 · see citing works
Campirán-Martínez, A., Jančík, V., Martı́nez-Otero, D., Hernández‐Balderas, U., Zavala‐Segovia, N., & Moya‐Cabrera, M. (2020) · Organometallics · doi:10.1021/acs.organomet.0c00096 · Cited by 6 · see citing works
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Al‐Khafaji, Y., Alrazzak, N. A., Saad, S. T., Abbas, A. S., & Merdan, M. G. (2019) · Journal of Physics Conference Series · doi:10.1088/1742-6596/1234/1/012055 · Cited by 5 · see citing works
Wang, P., Su, Z., Yang, Z., Cheng, J., Yang, H., Kibeye, I. M., & Chen, X. (2025) · Polymer Chemistry · doi:10.1039/d5py00481k
Lee, Y.-J., Teja, M. R., Yang, C.-Y., Halima, T. B., Ding, S., Tseng, H., Chen, H., & Lin, C. (2026) · Polymer · doi:10.1016/j.polymer.2026.130984
- Authors
- Han, H.-L., Liu, Y., Liu, J.-Y., Nomura, K., & Li, Y.-S.
- Affiliations
- Chinese Academy of Sciences (CN)
- Tokyo Metropolitan University (JP)
- Corresponding author
- Liu, Jing-Yu
- Venue
- Dalton Transactions
- Publisher
- Royal Society of Chemistry (RSC)
- Published
- 2013
- Volume
- 42
- Issue
- 34
- Pages
- 12346
- ISSN
- 1477-9226 (ISSN-L)
- 1477-9234
- OpenAlex
- W2124052734
- Cited by
- 41
- References
- 48
- Citations by year
- 2026: 2 · 2025: 1 · 2024: 1 · 2023: 1 · 2022: 2 · 2021: 1 · 2020: 4 · 2019: 5 · 2018: 2 · 2017: 9 · 2016: 3 · 2015: 4 · 2014: 6
- FWCI
- 1.65
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Dalton Transactions (publishedVersion)
- PubMed (publishedVersion)
- Funders
- National Natural Science Foundation of China
- Topics
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Physical Sciences › Chemical Engineering › Process Chemistry and Technology › Carbon dioxide utilization in catalysis
- Physical Sciences › Chemistry › Organic Chemistry › Organometallic Complex Synthesis and Catalysis
- Keywords
- ε-caprolactone, ring-opening polymerization, catalyst precursors, living polymerization, adamantyl substituents, polycaprolactone
- MeSH terms
- Aluminum, Caproates, Catalysis, Lactones, Molecular Conformation, Organometallic Compounds, Crystallography, X-Ray, Coordination Complexes, Polymerization
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