Abstract
A series of methylene-bridged salicylaldiminato tridentate [ONS] ligands bearing different alkylthio sidearms and the corresponding binuclear titanium complexes (Ti 2 a, Ti 2 b, Ti 2 c) were synthesized and characterized by elemental analysis, ESI-MS, FT IR, 1H and 13C NMR. To the best of our knowledge, these were the first non-metallocene tridentate binuclear Ti complexes reported. When activated by modified methylaluminoxane (MMAO), these binuclear Ti complexes displayed extremely high activities in the range of 106 g mol−1 h−1 atm−1 for ethylene polymerization and ethylene/α-olefins copolymerization at atmospheric pressure, producing high molecular weight polymers with narrow polydispersity. Both the catalytic behavior and the spectroscopic characterization indicated that the catalysts assumed symmetric structure and contained single-site active species. Most importantly, the catalytic activities towards ethylene (co)polymerization as well as comonomer incorporation ratios were much higher than that of the corresponding mononuclear complexes. Meanwhile, the properties of polymers and the comonomer incorporation ratios can be effectively tuned by the reaction conditions and the alkylthio side group on ligands. Complex Ti 2 c bearing the long octylthio sidearm showed significantly higher activity for ethylene polymerization than the methylthio functionalized Ti 2 a, presumably due to the increased solubility of the catalyst in the reaction medium. While for copolymerization, complex Ti 2 a demonstrated the highest catalytic activity and comonomer incorporation ratio, due the small steric hindrance of the methylthio side group.
Graphical Abstract
Similar content being viewed by others
References
Natta G, Danusso F (eds) (1967) Stereoregular polymers and stereospecific polymerizations. Pergamon Press, Oxford
Kaminsky W (2004) J Polym Sci Part A 42:3911–3921
Ittel SD, Johnson LK, Brookhart M (2000) Chem Rev 100:1169–1204
Bourget-Merle L, Lappert MF, Severn JR (2002) Chem Rev 102:3031–3065
Gibson VC, Redshaw C, Solan GA (2007) Chem Rev 107:1745–1776
Nomura K, Zhang S (2011) Chem Rev 111:2342–2362
Budagumpi S, Kim KH, Kim I (2011) Coord Chem Rev 255:2785–2809
Wang J, Nan F, Guo J, Wang J, Shi X, Huang H, Huang Q, Yang W (2016) Catal Lett 146:609–619
Breuil PAR, Magna L, Olivier-Bourbigou H (2015) Catal Lett 145:173–192
Netalkar SP, Netalkar PP, Sathisha MP, Budagumpi S, Revankar VK (2014) Catal Lett 144:181–191
Stalzer MM, Delferro M, Marks TJ (2015) Catal Lett 145:3–14
Yoshida Y, Mohri J, Ishii S, Mitani M, Saito J, Matsui S, Makio H, Nakano T, Tanaka H, Onda M, Yamamoto Y, Mizuno A, Fujita T (2004) J Am Chem Soc 126:12023–12032
Kashiwa N, Fujita T (2001) J Am Chem Soc 123:6847–6856
Makio H, Fujita T (2009) Acc Chem Res 42:1532–1544
Matsugi T, Fujita T (2008) Chem Soc Rev 37:1264–1277
Makio H, Terao H, Iwashita A, Fujita T (2011) Chem Rev 111:2363–2449
Iwashita A, Chan MCW, Makio H, Fujita T (2014) Catal Sci Technol 4:599–610
Xie G, Qian C (2008) J Polym Sci A: Polym Chem 46:211–217
Xie G, Li Y, Sun J, Qian C (2009) Inorg Chem Commun 12:796–799
Xie G, Li T, Zhang A (2010) Inorg Chem Commun 13:1199–1202
Xie G, Liu G, Li L, Li T, Zhang A, Feng J (2014) Catal Commun 45:7–10
Xie G, Zhang X, Li T, Li L, Liu G, Zhang A (2014) J Mol Catal A Chem 383–384:121–127
Xie G, Song W, Li T, Xu X, Lan Z, Li Y, Zhang A (2014) J Appl Polym Sci 131:41178
Li T, Song W, Ai H, You Q, Zhang A, Xie G (2015) J Polym Res 22:631
Redshaw C, Tang Y (2012) Chem Soc Rev 41:4484–4510
Hu WQ, Sun XL, Wang C, Tang Y, Shi LP, Xia W, Sun J, Dai HL, Li XX, Yao XL, Wang XR (2004) Organometallics 23:1684–1688
Wang C, Sun, XL, Guo YH, Gao Y, Liu B, Ma Z, Xia W, Shi LP, Tang Y (2005) Macromol Rapid Commun 26:1609–1614
Wang C, Ma Z, Sun XL, Gao Y, Guo YH, Tang Y, Shi LP (2006) Organometallics 25:3259–3266
Gao ML, Gu YF, Wang C, Yao XL, Sun XL, Li CF, Qian CT, Liu B, Ma Z, Tang Y, Xie ZW, Bu SZ, Gao Y (2008) J Mol Catal A Chem 292:62
Gao ML, Sun XL, Gu YF, Yao XL, Li CF, Bai JY, Wang C, Ma Z, Tang Y, Xie ZW, Bu SZ, Qian CT (2008) J Poly Sci Part A 46:2807–2819
Li L, Metz MV, Li H, Chen MC, Marks TJ, Liable-Sands L, Rheingold AL J Am Chem Soc 124:12725–12741
Guo N, Li L, Marks TJ (2004) J Am Chem Soc 126:6542–6543
Li H, Li L, Marks TJ (2004) Angew Chem Int Ed 43:4937–4940
Li H, Marks TJ (2006) PNAS 103:15295–15302
Salata MR, Marks TJ (2008) J Am Chem Soc 130:12–13
Salata MR, Marks TJ (2009) Macromolecules 42:1920–1933
Rodriguez BA, Delferro M, Marks TJ (2009) J Am Chem Soc 131:5902–5919
Delferro M, Marks TJ (2011) Chem Rev 111:2450–2485
Liu SF, Motta A, Delferro M, Marks TJ (2013) J Am Chem Soc 135:8830–8833
McInnis JP, Delferro M, Marks TJ (2014) Acc Chem Res 47:2545–2557
Liu SF, Motta A, Mouat AR, Delferro M, Marks TJ (2014) J Am Chem Soc 136:10460–10469
Bratko I, Gómez M (2013) Dalton Trans 42:10664–10681
Buchwalter P, Rosé J, Braunstein P (2015) Chem Rev 115:28–126
Radlauer MR, Day MW, Agapie T (2012) J Am Chem Soc 134:1478–1481
Radlauer MR, Buckley AK, Henling LM, Agapie T (2013) J Am Chem Soc 135:3784–3787
Takeuchi D (2010) Dalton Trans 39:311–328
Sachse A, Demeshko S, Dechert S, Daebel V, Lange A, Meyer F (2010) Dalton Trans 39:3903–3914
Hu T, Tang LM, Li XF, Li YS, Hu NH (2005) Organometallics 24:2628–2632
Zhang S, Vystorop I, Tang Z, Sun WH (2007) Organometallics 26:2456–2460
Huang YB, Tang GR, Jin GY, Jin JX (2008) Organometallics 27:259–269
Chen Q, Yu J, Huang J (2007) Organometallics 26:617–625
Luo S, Shen B, Li B, Song H, Xu S, Wang B (2009) Organometallics 28:3109–3112
Kuwabara J, Takeuchi D, Osakada K (2006) Chem Commun 36:3815–3817
Han SL, Yao ED, Qin W, Zhang SF, Ma YG (2012) Macromolecules 45:4054–4059
Canali L, Cowan E (2000) J Chem Sci Perkin Trans 13:2055–2066
Yang XH, Wang Z, Sun XL, Tang Y (2009) Dalton Trans 8945–8954
Acknowledgements
The authors are grateful for the financial support from the Natural Sciences Foundation of China (21172269).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Li, T., Lan, Z., Xie, G. et al. Binuclear Titanium Catalysts Based on Methylene-Bridged Tridentate Salicylaldiminato Ligands for Ethylene Homo- and Copolymerization. Catal Lett 147, 996–1005 (2017). https://doi.org/10.1007/s10562-017-1985-9
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10562-017-1985-9