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Bulk polymerization of rac-lactide initiated by guanidinate alkoxide complexes of rare earth metals. The molecular structure of the cluster [{(Me3Si)2NC(NPri)2}Nd]4(μ3-OPri)8Li7(μ2-Cl)3(μ3-Cl)2(μ4-Cl)2

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Abstract

The complexes {(Me3Si)2NC(NPri)2}2LnOBut (Ln = Y (1), Lu (2)) initiate the bulk polymerization of racemic lactide (LA) at 130 °C. At the monomer: initiator molar ratio ([LA]: 1) equal to 1000: 1, the quantitative conversion of the monomer is achieved within 6 h. The resulting polymers are characterized by a rather narrow monomodal molecular weight distribution (M w/M n = 1.46–1.82) and molecular weights up to 33400 g mol−1. The molecular weights of the resulting polylactides measured by gel permeation chromatography are 3–11 times lower than the values calculated from the monomer: initiator ratio on the assumption of one growing polymer chain per catalytic center. The reaction of the in-situ prepared complex [(Me3Si)2NC(NPri)2]NdCl2 with 2 equiv. of PriOLi produced the 11-nuclear cluster [{(Me3Si)2NC(NPri)2}Nd]4(μ3-OPri)8Li7(μ2-Cl)3(μ3-Cl)2(μ4-Cl)2 (3), which was isolated in 62% yield. The structure of compound 3 was established by X-ray diffraction. Complex 3 initiates both the bulk and solution polymerization of rac-lactide. In the bulk polymerization at the molar ratio [LA]: [Nd] = 500: 1, the 89% conversion of the monomer was achieved within one hour. The polylactide thus synthesized has the molecular weight M n = 19720 g mol−1 and a rather narrow polydispersity M w/M n = 1.54.

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References

  1. A. P. Gupta, V. Kumar, Eur. Polym. J., 2007, 43, 4053.

    Article  CAS  Google Scholar 

  2. A.-C. Albertsson, I. K. Varma, Biomacromolecules, 2003, 4, 1466.

    Article  CAS  Google Scholar 

  3. X. Pang, X. Zhuang, Z. Tang, X. Chen, Biotechnol. J., 2010, 5, 1125.

    Article  CAS  Google Scholar 

  4. R. Auras, B. Harte, S. Selke, Macromol. Biosci., 2004, 4, 835.

    Article  CAS  Google Scholar 

  5. R. Drumright, P. Gruber, D. Henton, Adv. Mater., 2000, 12, 1841.

    Article  CAS  Google Scholar 

  6. C.-S. Ha, J. A. Gardella, Chem. Rev., 2005, 105, 4205.

    Article  CAS  Google Scholar 

  7. O. Dechy-Cabaret, B. Martin-Vaca, D. Bourissou, Chem. Rev., 2004, 104, 6147.

    Article  CAS  Google Scholar 

  8. A. Amgoune, C. M. Thomas, J.-F. Carpentier, Pure Appl. Chem. 79, 2013.

  9. B. J. O’Keefe, M. A. Hillmyer, W. B. Tolman, J. Chem. Soc., Dalton Trans., 2001, 2215.

    Google Scholar 

  10. R. H. Platel, L. M. Hodgson, C. K. Williams, Polym. Rev., 2008, 48, 11.

    Article  CAS  Google Scholar 

  11. S. Pencze, M. Cypryk, A. Duda, P. Kubisa, S. Slomkowski, Prog. Polym. Sci., 2007, 32, 247.

    Article  Google Scholar 

  12. V. Poirier, T. Roisnel, S. Sinbandhit, M. Bochmann, J.-F. Carpentier, Y. Sarazin, Chem. A Eur. J., 2012, 18, 2998.

    Article  CAS  Google Scholar 

  13. H. Yasuda, Top. Organomet. Chem., 1999, 255.

    Google Scholar 

  14. N. Ajellal, J.-F. Carpentier, C. Guillaume, S. M. Guillaume, M. Helou, V. Poirier, Y. Sarazin, A. A. Trifonov, J. Chem. Soc., Dalton Trans., 2010, 39, 8363.

    Article  CAS  Google Scholar 

  15. X. Liu, X. Shang, T. Tang, N. Hu, F. Pei, D. Cui, X. Chen, X. Jing, Organometallics, 2007, 26, 2747.

    Article  Google Scholar 

  16. H. Sheng, F. Xu, Y. Yao, Y. Zhang, Q. Shen, Inorg. Chem., 2007, 46, 7722.

    Article  CAS  Google Scholar 

  17. T.-P.-A. Cao, A. Buchard, X. F. Le Goff, A. Auffrant, C. K. Williams, Inorg. Chem., 2012, 51, 2157.

    Article  CAS  Google Scholar 

  18. R. D. Shannon, Acta Crystallogr., Sect. A, 1976, 32, 751.

    Article  Google Scholar 

  19. N. Ajellal, D. M. Lyubov, M. A. Sinenkov, G. K. Fukin, A. V. Cherkasov, C. M. Thomas, J.-F. Carpentier, A. A. Trifonov, Chem. Eur. J., 2008, 14, 5440.

    Article  CAS  Google Scholar 

  20. J. Chen, Y. Yao, Y. J. Luo, L. Y. Zhou, Y. Zhang, Q. Shen, J. Organomet. Chem., 2004, 689, 1019.

    Article  CAS  Google Scholar 

  21. L. Zhou, Y. Yao, Y. Zhang, M. Xue, J. Chen, Q. Shen, Eur. J. Inorg. Chem., 2004, 2167.

    Google Scholar 

  22. M. N. Bochkarev, A. A. Maleev, T. V. Balashova, G. K. Fukin, E. V. Baranov, Y. A. Efimova, B. I. Petrov, V. A. Ilichev, Inorg. Chim. Acta, 2008, 361, 2533.

    Article  CAS  Google Scholar 

  23. F. Feil, S. Harder, Eur. J. Inorg. Chem., 2005, 4438.

    Google Scholar 

  24. T. V. Mahrova, G. K. Fukin, A. V. Cherkasov, A. A. Trifonov, N. Ajellal, J.-F. Carpentier, Inorg. Chem., 2009, 48, 4258.

    Article  CAS  Google Scholar 

  25. G. G. Skvortsov, M. V. Yakovenko, P. M. Castro, G. K. Fukin, A. V. Cherkasov, J.-F. Carpentier, A. A. Trifonov, Eur. J. Inorg. Chem., 2007, 3260.

    Google Scholar 

  26. C. Qian, X. Zhang, J. Li, F. Xu, Y. Zhang, Q. Shen, Organometallics, 2009, 28, 3856.

    Article  CAS  Google Scholar 

  27. G. Helgesson, S. Jagner, Polyhedron, 1991, 10, 1559.

    Article  CAS  Google Scholar 

  28. M. D. Taylor, C. P. Carter, J. Inorg. Nucl. Chem., 1962, 24, 387.

    Article  CAS  Google Scholar 

  29. L. E. Manzer, Inorg. Chem., 1978, 17, 1552.

    Article  CAS  Google Scholar 

  30. H. Ma, J. Okuda, Macromolecules, 2005, 38, 2665.

    Article  CAS  Google Scholar 

  31. M. Save, M. Schappacher, A. Soum, Macromol. Chem. Phys., 2002, 203, 889.

    Article  CAS  Google Scholar 

  32. G. M. Sheldrick, SHELXTL v. 6.12, Structure Determination Software Suite, Bruker AXS, Madison, Wisconsin, USA, 2000.

    Google Scholar 

  33. G. M. Sheldrick, SADABS v. 2.01, Bruker/Siemens Area Detector Absorption Correction Program, Bruker AXS, Madison, Wisconsin, USA, 1998.

    Google Scholar 

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Authors and Affiliations

  1. G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, 49 ul. Tropinina, 603950, Nizhny Novgorod, Russian Federation

    M. A. Sinenkov, T. A. Glukhova, A. V. Cherkasov & A. A. Trifonov

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  1. M. A. Sinenkov
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  2. T. A. Glukhova
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  3. A. V. Cherkasov
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  4. A. A. Trifonov
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Correspondence to A. A. Trifonov.

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Dedicated to Academician of the Russian Academy of Sciences I. P. Beletskaya on the occasion of her anniversary.

Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 0722–0730, March, 2013.

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Sinenkov, M.A., Glukhova, T.A., Cherkasov, A.V. et al. Bulk polymerization of rac-lactide initiated by guanidinate alkoxide complexes of rare earth metals. The molecular structure of the cluster [{(Me3Si)2NC(NPri)2}Nd]4(μ3-OPri)8Li7(μ2-Cl)3(μ3-Cl)2(μ4-Cl)2 . Russ Chem Bull 62, 722–730 (2013). https://doi.org/10.1007/s11172-013-0099-9

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  • DOI: https://doi.org/10.1007/s11172-013-0099-9

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