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A New Class of Pyridine-Amide Containing Ti and Zr Based Catalysts for Olefin Polymerization: Influence of Ligand Substituents

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Abstract

Two tridendate pyridine-amide ligands in di-deprotonated form have been used to synthesize new titanium and zirconium complexes. The molecular structure of pentafluoro containing Titanium and Zirconium complexes were determined by DFT calculations. These new metal complexes have been further evaluated for ethylene polymerization activity in the presence of co-catalyst methylaluminoxane (MAO) under atmospheric pressure, producing polyethylenes with moderate molecular weights and unimodal molecular weight distribution. Remarkably, zirconium complexes show higher activity than titanium complexes under the same polymerization condition. The catalytic activity of all the complexes were found to be temperature dependent and reach their highest efficiency at 70 °C. The influence of the nature of the ligands and reaction parameters upon the catalytic activities has been studied. Additionally, the pentafluoro containing Zirconium and Titanium complexes were further evaluated for the copolymerization of ethylene and propylene and exhibited good catalytic activity.

Graphic Abstract

A new class of titanium and zirconium based metal complexes were synthesised from pyridine-amide containing ligands. The synthesised complexes have been evaluated for ethylene polymerization in the presence of co-catalyst methylaluminoxane (MAO) under atmospheric pressure. Interestingly, zirconium complexes show high catalytic activities than titanium complexes under the same polymerization condition.

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References

  1. Rajput A, Mukherjee R (2013) Coord Chem Rev 257:350

    CAS  Google Scholar 

  2. Rose MJ, Mascharak PK (2008) Coord Chem Rev 252:2093

    CAS  PubMed  PubMed Central  Google Scholar 

  3. Mishra A, Gupta R (2014) Dalton Trans 43:7668

    CAS  PubMed  Google Scholar 

  4. Mishra A, Kang SC, Chi K-W (2013) Eur J Inorg Chem 30:5222–5232

    Google Scholar 

  5. Ray M, Ghosh D, Shirin Z, Mukherjee R (1997) Inorg Chem 36:3568

    CAS  PubMed  Google Scholar 

  6. Mishra A, Lee S, Kim H, Cook TR, Stang PJ, Chi K-W (2012) Chem Asian J 7:2592

    CAS  PubMed  PubMed Central  Google Scholar 

  7. Mishra A, Jung H, Lee MH, Lah MS, Chi K-W (2013) Inorg Chem 52:8573

    CAS  PubMed  Google Scholar 

  8. Mishra A, Ravikumar S, Hong SH, Kim H, Vajpayee V, Lee HW, Ahn BC, Wang M, Stang PJ, Chi K-W (2011) Organometallics 30:6343

    CAS  PubMed  PubMed Central  Google Scholar 

  9. Mishra A, Lee SC, Kaushik N, Cook TR, Choi EH, Kaushik NK, Stang PJ, Chi K-W (2014) Chem Eur J 20:14410

    CAS  PubMed  Google Scholar 

  10. Mishra A, Ravikumar S, Song Y, Prabhu NS, Hong SH, Kim H, Cheon S, Noh J, Chi K-W (2014) Dalton Trans 43:6032

    CAS  PubMed  Google Scholar 

  11. Mishra A, Jeong YJ, Jo J-H, Kang SC, Kim H, Chi K-W (2014) Organometallics 33:1144

    CAS  Google Scholar 

  12. Mishra A, Jeong YJ, Jo J-H, Kang SC, Lah MS, Chi K-W (2014) ChemBioChem 15:695

    CAS  PubMed  Google Scholar 

  13. Mishra A, Ali A, Upreti S, Whittingham MS, Gupta R (2009) Inorg Chem 48:5234

    CAS  PubMed  Google Scholar 

  14. Mishra A, Kaushik NK, Verma AK, Gupta R (2008) Eur J Med Chem 43:2189

    CAS  PubMed  Google Scholar 

  15. Mishra A, Jo J-H, Kim H, Woo S, Chi K-W (2014) ChemPlusChem 79:925

    CAS  Google Scholar 

  16. Srivastava S, Dagur MS, Ali A, Gupta R (2015) Dalton Trans 44:17453

    CAS  PubMed  Google Scholar 

  17. Jacob W, Mukherjee R (2006) Inorg Chim Acta 359:4565

    CAS  Google Scholar 

  18. Marcos D, Folgado JV, Beletran-Porter D, Prado-Gambardella D, Pulcinelli SH, De Almeida-Santos RH (1990) Polyhedron 9:2699

    CAS  Google Scholar 

  19. Kumar S, Munjal M, Singh J, Gupta R (2014) Eur J Inorg Chem 29:4957–4965

    Google Scholar 

  20. Marcos D, Martınez-Manez R, Folgado JV, Beltra-Porter D, Fuertes A (1989) Inorg Chim Acta 159:11

    CAS  Google Scholar 

  21. Das A, Peng S-M, Lee G-H, Bhattacharya S (2004) New J Chem 28:712

    CAS  Google Scholar 

  22. Mishra A, Prabhu P, Gocher C, Gupta V (2019) ChemistrySelect 4:3286

    CAS  Google Scholar 

  23. Makio H, Terao H, Iwashita A, Fujita T (2011) Chem Rev 111:2363

    CAS  PubMed  Google Scholar 

  24. Nomura K, Liu J, Padmanabhan S, Kitiyanan BJ (2007) Mol Catal A Chem 267:1

    CAS  Google Scholar 

  25. Murray RE, George VM, Nowlin DL, Schultz CC, Petersen JL (2002) Polym Prepr 43:294

    CAS  Google Scholar 

  26. Scollard JD, McConville DH (1996) J Am Chem Soc 118:10008

    CAS  Google Scholar 

  27. Terao H, Iwashita A, Matsukawa N, Ishii S, Mitani M, Tanaka H, Nakano T, Fujita T (2011) ACS Catal 1:254

    CAS  Google Scholar 

  28. Li H, Xu B, He J, Liu X, Gao W, Mu Y (2015) Chem Commun 51:16703

    CAS  Google Scholar 

  29. Cozzi PG, Gallo E, Floriani C, Chiesi-Villa A, Rizzoli C (1995) Organometallics 14:4994

    CAS  Google Scholar 

  30. Gao Y, Aidan R, Mouat A, Motta A, Macchioni C, Zuccaccia, Delferro M, Marks TJ (2015) ACS Catal 5:5272

    CAS  Google Scholar 

  31. Boussie TR, Diamond GM, Goh C, Hall KA, LaPointe AM, Leclerc MK, Murphy V, Shoemaker JAW, Turner H, Rosen RK, Stevens JC, Alfano F, Busico V, Cipullo R, Talarico G (2006) Angew Chem Int Ed 45:3278

    CAS  Google Scholar 

  32. Gurubasavaraj PM, Nomura K (2010) Organometallics 29:3500

    CAS  Google Scholar 

  33. Tewasekson U, Tsutsumi K, Nomura K (2016) Organometallics 35:866

    CAS  Google Scholar 

  34. Takii Y, Inagaki A, Nomura K (2013) Dalton Trans 42:11632

    CAS  PubMed  Google Scholar 

  35. Xu W, Guo Y, Wei Y, Fu Z, Fan Z (2019) Catal Commun 120:6

    CAS  Google Scholar 

  36. Bergamo AL, das Chagas RP, de Casagrande L (2013) Catal Commun 42:113

    CAS  Google Scholar 

  37. Resconi L, Camurati I, Sudmeijer O (1999) Top Catal 7:145

    CAS  Google Scholar 

  38. Resconi L, Cavallo L, Fait A, Piemontesi F (2000) Chem Rev 100:1253

    CAS  PubMed  Google Scholar 

  39. Talarico G, Budzelaar PHM (2006) J Am Chem Soc 128:4524

    CAS  PubMed  Google Scholar 

  40. Wright LA, Hope EG, Solan GA, Cross WB, Singh K (2016) Organometallics 35:1183

    CAS  Google Scholar 

  41. Ayoub ED, Takase MK, Henling LM, Labinger JA, Bercaw JE (2015) Organometallics 34:4707

    Google Scholar 

  42. Golisz SR, Bercaw JE (2009) Macromolecules 42:8751

    CAS  Google Scholar 

  43. Mishra A, Ali A, Upreti S, Gupta R (2008) Inorg Chem 47:154

    CAS  PubMed  Google Scholar 

  44. Frisch MJ, Truncks GW, Schlegel HB (2007) GAUSSIAN 03, Revision E.01, Gaussian: Wallingford, CT

  45. Britovsek JP, Gibson VC, Hoarau OD, Spitzmesser SK, White AJP, Williams DJ (2003) Inorg Chem 42:3454

    CAS  PubMed  Google Scholar 

  46. Kaji A, Akimoto Y, Murano M (1991) J Polym Sci A 29:1987

    CAS  Google Scholar 

  47. Stürzel M, Mihan S, Mülhaupt R (2016) Chem Rev 116:1398

    PubMed  Google Scholar 

Download references

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Correspondence to Virendra Kumar Gupta.

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Mishra, A., Bhajiwala, H., Kothari, A. et al. A New Class of Pyridine-Amide Containing Ti and Zr Based Catalysts for Olefin Polymerization: Influence of Ligand Substituents. Catal Lett 149, 3425–3431 (2019). https://doi.org/10.1007/s10562-019-02907-3

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