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A kinetic and spectroscopic study on the polyoxometalate species in a reaction-controlled phase transfer catalytic epoxidation system

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Abstract

An excellent catalytic epoxidation system containing [π-C5H5N(CH2)15CH3]3[PW4O32]/H2O2/ethyl acetate/olefin has been prepared and shown to exhibit a unique reaction-controlled phase transfer behavior. The composition and structural changes of the catalyst [π-C5H5N(CH2)15CH3]3[PW4O32] (I) before, during and after reaction were investigated by 31P NMR, 31P MAS NMR, 183W NMR, IR, Raman and UV–Vis spectroscopy. The 31P MAS NMR and 31P NMR confirmed that the original catalyst was a mixture of heteropoly tungstophosphates. According to the 31P NMR and 183W NMR analysis, new phosphoperoxotungstate species, [PWxOy]z−, were produced in this catalytic system instead of the well known species of {PO4[WO(O2)2]4}3−. The active species of phosphoperoxotungstate containing many peroxo bonds should be similar to [(PO4){WO(O2)2}4]3−. The species degraded from H3PW12O40, H2O2 and quaternary ammonium were very complicated and the compositions were mainly dependent on the ratio of H2O2 to H3PW12O40.

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References

  1. Okuhara T, Mizuno N, Misono M (1996) Adv Catal 41:113

    Article  CAS  Google Scholar 

  2. Grigoropoulou G, Clark JH, Elings JA (2003) Green Chem 1:5

    Google Scholar 

  3. Hill CL (2004) Angew Chem Int Ed 43:402

    Article  CAS  Google Scholar 

  4. Klawonn M, Tse MK, Bhor S, Döbler C, Beller M (2004) J Mol Catal A 218:13

    Article  CAS  Google Scholar 

  5. Sakamoto T, Pac C (2000) Tetrahedron Lett 41:10009

    Article  CAS  Google Scholar 

  6. Notari B (1996) Adv Catal 41:253

    Article  CAS  Google Scholar 

  7. Ding Y, Gao Q, Wang B, Li G, Yan L, Suo J (2005) J Porous Mater 12:131

    Article  CAS  Google Scholar 

  8. Liu P, Wang H, Feng Z, Ying P, Li C (2008) J Catal 256:345

    Article  CAS  Google Scholar 

  9. Salles L, Aubry C, Robert F, Chottard G, Thouvenot R, Ledon H, Brégeault J-M (1993) New J Chem 17:367

    CAS  Google Scholar 

  10. Herrmann WA, Fischer RW, Marz DW (1991) Angew Chem Int Ed Engl 30:1638

    Article  Google Scholar 

  11. Kozhevnikov IV (1998) Chem Rev 98:171

    Article  CAS  Google Scholar 

  12. Arends IWCE, Sheldon RA (2002) Top Catal 19:133

    Article  CAS  Google Scholar 

  13. Venturello C, Alneri E, Ricci M (1983) J Org Chem 48:3831

    Article  CAS  Google Scholar 

  14. Venturello C, D’Aloisio R, Bart JCJ, Ricci M (1985) J Mol Catal 32:107

    Article  CAS  Google Scholar 

  15. Venturello C, D’Aloisio R (1988) J Org Chem 53:1553

    Article  CAS  Google Scholar 

  16. Matoba Y, Inoue H, Akagi J, Okabayashi T, Ishii Y, Ogawa M (1984) Synth Commun 14:865

    Article  CAS  Google Scholar 

  17. Ishii Y, Yamawaki K, Ura T, Yamada H, Yoshida T, Ogawa M (1988) J Org Chem 53:3587

    Article  CAS  Google Scholar 

  18. Yamamoto H, Tsuda M, Sakaguchi S, Ishii Y (1997) J Org Chem 62:7174

    Article  CAS  Google Scholar 

  19. Sato K, Aoki M, Ogawa M, Hashimoto T, Noyori R (1996) J Org Chem 61:8310

    Article  CAS  Google Scholar 

  20. Noyori R, Aoki M, Sato K (2003) Chem Commun 1977

  21. Kamata K, Yonehara K, Sumida Y, Yamaguchi K, Hikicchi S, Mizuno N (2003) Science 300:964

    Article  CAS  Google Scholar 

  22. Nakagawa Y, Kamata K, Kotani M, Yamaguchi K, Mizuno N (2005) Angew Chem Int Ed Engl 44:5136

    Article  CAS  Google Scholar 

  23. Neumann R, Gara M (1994) J Am Chem Soc 116:5509

    Article  CAS  Google Scholar 

  24. Csanyi LJ, Jaky K (1991) J Catal 127:42

    Article  CAS  Google Scholar 

  25. Ballistreri FP, Bazzo A, Tomaselli GA, Toscano RM (1992) J Org Chem 57:7074

    Article  CAS  Google Scholar 

  26. Aubry C, Chottard G, Platzer N, Bregeault JM, Thouvenot R, Chauveau F, Huet C, Ledon H (1991) Inorg Chem 30:4409

    Article  CAS  Google Scholar 

  27. Salles L, Aubry C, Thouvenot R, Robert F, Doremieux-Morin C, Chottard G, Ledon H, Jeanin Y, Bregeault JM (1994) Inorg Chem 33:871

    Article  CAS  Google Scholar 

  28. Salles L, Piquemal JY, Thouvenot R, Minot C, Bregeault JM (1997) J Mol Catal A 117:375

    Article  CAS  Google Scholar 

  29. Gresley NM, Griffith WP, Laemmel AC, Nogueira HIC, Parkin BC (1997) J Mol Catal A 117:185

    Article  CAS  Google Scholar 

  30. Griffith WP, Parkin BC, White AJP, Williams DJ (1995) J Chem Soc Chem Commun 2183

  31. Campbell NJ, Dengel AC, Edwards CJ, Griffith WP (1989) J Chem Soc Dalton Trans 1203

  32. Ding Y, Gao Q, Li G, Zhang H, Wang J, Yan L, Suo J (2004) J Mol Catal A 218:161

    Article  CAS  Google Scholar 

  33. Ding Y, Ma B, Gao Q, Li G, Yan L, Suo J (2005) J Mol Catal A 230:121

    Article  CAS  Google Scholar 

  34. Ding Y, Ma B, Gao Q, Suo J (2006) J Chem Res 499

  35. Xi Z, Zhou N, Sun Y, Li K (2001) Science 292:1139

    Article  CAS  Google Scholar 

  36. Li J, Gao S, Li M, Zhang R, Xi Z (2004) J Mol Catal A 218:247

    Article  CAS  Google Scholar 

  37. Zhang S, Gao S, Xi Z, Xu J (2007) Catal Commun 8:531

    Article  CAS  Google Scholar 

  38. Duncan DC, Chambers RC, Hecht E, Hill CL (1995) J Am Chem Soc 117:681

    Article  CAS  Google Scholar 

  39. Zhao W, Ma B, Hua H, Zhang Y, Ding Y (2008) Catal Commun 9:2455

    Article  CAS  Google Scholar 

  40. Ding Y, Zhao W, Hua H, Ma B (2008) Green Chem 10:910

    Article  CAS  Google Scholar 

  41. Gao J, Chen Y, Han B, Feng Z, Li C, Zhou N, Gao S, Xi Z (2004) J Mol Catal A 210:197

    Article  CAS  Google Scholar 

  42. Chen Y, Zhuang J, Liu X, Gao J, Han X, Bao X, Zhou N, Gao S, Xi Z (2004) Catal Lett 93:41

    Article  CAS  Google Scholar 

  43. Hashimoto M, Itoh K, Lee KY, Misono M (2001) Top Catal 15:265

    Article  CAS  Google Scholar 

  44. Mahha Y, Salles L, Piquemal JY, Briot E, Atlamsani A, Brégeault JM (2007) J Catal 249:338

    Article  CAS  Google Scholar 

  45. Kovalchuk T, Sfihi H, Zaitsev V, Fraissard J (2007) J Catal 249:1

    Article  CAS  Google Scholar 

  46. Liu Y, Murata K, Hanaoka T, Inaba M, Sakanishi K (2007) J Catal 248:277

    Article  CAS  Google Scholar 

  47. Chen Y, Gong J, Qu L (2004) Coord Chem Rev 248:245

    Article  CAS  Google Scholar 

  48. Chen H, Dai W, Yang X, Gao R, Cao Y, Li H, Fan K (2006) Appl Catal A 309:62

    Article  CAS  Google Scholar 

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Acknowledgments

This work was supported by the National Natural Science Foundation of China (Grant No. 20803032) and the Natural Science Foundation of Nanyang Normal University (No. ZX2012012). The authors gratefully thank Prof. W. Wang for the measurement of solid state NMR, GC and his valuable discussions.

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Authors and Affiliations

  1. College of Chemistry and Pharmaceutical Engineering, Nanyang Normal University, Nanyang, 473061, China

    Wei Zhao

  2. Key Laboratory of Nonferrous Metals Chemistry and Resources Utilization of Gansu Province, State Key Laboratory of Applied Organic Chemistry and College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, 730000, China

    Yong Ding

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  1. Wei Zhao
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  2. Yong Ding
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Correspondence to Yong Ding.

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Zhao, W., Ding, Y. A kinetic and spectroscopic study on the polyoxometalate species in a reaction-controlled phase transfer catalytic epoxidation system. Reac Kinet Mech Cat 109, 509–524 (2013). https://doi.org/10.1007/s11144-013-0565-2

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  • DOI: https://doi.org/10.1007/s11144-013-0565-2

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