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Hydroformylation of Hex-1-ene by a Dinuclear gem-Dithiolato-bridged Rhodium Catalyst Under CO/H2O Conditions

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Abstract

In this work the results of the study of the catalytic activity of the dinuclear gem-dithiolato-bridged rhodium complex [Rh2(μ-S2CBn2)(cod)2] (Bn = benzyl; cod = 1,5-cyclooctadiene) for the hydroformylation of hex-1-ene in CO/H2O, are presented. Under the best conditions for hydroformylation [P(CO) = 22 atm at 80 °C, in 24 h, toluene/H2O = 8/2, v/v, hex-1-ene (3 mmol), [Rh] = 0.01 mmol, hex-1-ene/[Rh] = 15 molar ratio] the only organic products observed (detected by GC and GC-MS) were heptanal and 2-methylhexanal and traces of 2-hexene (isomerization product). In addition, the products of the water gas shift reaction, H2 and CO2, were also obtained as competitive reaction of the hydroformylation process.

Graphical Abstract

In this work, the hydroformylation of hex-1-ene in CO/H2O catalyzed by a dinuclear gem-dithiolato-bridged rhodium complex [Rh2(μ-S2CBn2)(cod)2] (Bn = benzyl; cod = 1,5-cyclooctadiene) dissolved in toluene is described. Under catalytic conditions the only organic products observed were heptanal and 2-methylhexanal and traces of 2-hexene. In addition, the products of the water gas shift reaction, H2 and CO2, were also observed.

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References

  1. Cornils B, Herrmann WA (2002) Applied homogeneous catalysis with organometallic compounds, 2nd edn. Wiley/VCH, Weinheim

    Google Scholar 

  2. Leighton JL (2005) In: Evans PA (ed) Modern rhodium-catalyzed organic reactions, Chap. 5. VCH, Weinheim

    Google Scholar 

  3. van Leeuwen PWNM, Claver C (2000) In: James BR, van Leeuwen PWNM (eds) Rhodium catalyzed hydroformylation, catalysis by metal complexes series, vol 22. Kluwer, Dordrecht

    Google Scholar 

  4. Jacobs G, Davis BH (2007) Low temperature water–gas shift catalysts in: Catalysis, Spivey JJ, Dooley KM (eds) vol 20, RSC Publishing, Cambridge, p. 122

  5. Kiss G (2001) Chem Rev 101:3435

    Article  CAS  Google Scholar 

  6. Pardey AJ, Hung-Low F, Uzcategui GC, Ortega MC, Longo C (2006) React Kinet Catal Lett 88:203

    Article  CAS  Google Scholar 

  7. Cabrera A, Sharma P, Garcia JL, Velasco L, Perez FJ, Arias JL, Rosas N (1997) J Mol Catal A 118:67

    Google Scholar 

  8. Escaffre P, Thorez A, Kalck P (1985) J Mol Catal 33:87

    Article  CAS  Google Scholar 

  9. Fachinetti G, Funaioli T, Marchetti F (2005) Chem Commun 2912

  10. Kang H, Mauldin CH, Cole T, Slegeir W, Cann K, Pettit R (1977) J Am Chem Soc 99:8323

    Article  CAS  Google Scholar 

  11. Ford PC, Rokicki A (1988) Adv Organomet Chem 28:39

    Google Scholar 

  12. Laine RM (1978) J Am Chem Soc 100:451

    Google Scholar 

  13. Nomura K (1998) J Mol Catal A 130:1

    Article  CAS  Google Scholar 

  14. Ragani F, Cenini S (1996) J Mol Catal A 105:145

    Article  Google Scholar 

  15. Tafesh AM, Weiguny J (1996) Chem Rev 96:2035

    Article  CAS  Google Scholar 

  16. Joh T, Fujiwara K, Takahashi S (1993) Bull Chem Soc Jpn 66:978

    Article  CAS  Google Scholar 

  17. Linares C, Mediavilla M, Pardey AJ, Baricelli P, Longo-Pardey C, Moya SA (1998) Catal Lett 50:183

    Article  CAS  Google Scholar 

  18. Pardey AJ, Fernandez M, Alvarez J, Urbina C, Moronta D, Leon V, Longo C, Baricelli PJ, Moya SA (2000) J Mol Catal A 164:25

    Article  Google Scholar 

  19. Mdleleni MM, Rinker RG, Ford PC (1998) Inorg Chim Acta 270:345

    Article  CAS  Google Scholar 

  20. Pardey AJ, Uzcátegui GC, Hung-Low F, Rivas AB, Yánez JE, Ortega MC, Alvarez J, Longo C, Aguirre P, Moya SA (2005) J Mol Catal A 239:205

    Article  CAS  Google Scholar 

  21. Kalck P, Frances JM, Pfister PM, Southern TG, Thorez A (1983) J Chem Soc Chem Commun 510

  22. Kalck P (1987) In: de Meijere A, Dick HT (eds) Organometallics in organic synthesesm. Springer, Weinheim, p 297

    Google Scholar 

  23. Bayón JC, Claver C, Masdeu-Bultó AM (1999) Coord Chem Rev 193–195:73

    Article  Google Scholar 

  24. Escaffre P, Thorez A, Kalck P (1987) J Chem Soc Chem Commun 146

  25. Escaffre P, Thorez A, Kalck P (1987) New J Chem 11:601

    CAS  Google Scholar 

  26. Kalck P (1989) Pure Appl Chem 61:967

    Article  CAS  Google Scholar 

  27. Hernandez-Gruel MAF, Gracia-Arruego G, Rivas AB, Dobrinovich IT, Lahoz FJ, Pardey AJ, Oro LA, Pérez-Torrente JJ (2007) Eur J Inorg Chem:5677

  28. Rivas AB, Gascón JM, Lahoz FJ, Pardey AJ, Oro LA, Pérez-Torrente JJ (2008) Inorg Chem 47:6090

    Article  CAS  Google Scholar 

  29. Rivas AB, Pérez-Torrente JJ, Pardey AJ, Masdeu-Bultó AM, Dieguez M, Oro LA (2008) J Mol Catal A 300:121

    Google Scholar 

  30. Pardey AJ, Fernández M, Canestrari M, Baricelli P, Lujano E, Longo C, Sartori R, Moya SA (1999) React Kinet Catal Lett 67:325

    Article  CAS  Google Scholar 

  31. Pardey AJ, Fernández M, Moreno MA, Alvarez J, Mendez B, Rivas AB, Ortega MC, Baricelli P, Longo C (2000) React Kinet Catal Lett 70:293

    Article  CAS  Google Scholar 

  32. Pardey AJ, Ford PC (1989) J Mol Catal 53:247

    Article  CAS  Google Scholar 

  33. Laine RM (1982) J Mol Catal 14:137

    Article  CAS  Google Scholar 

  34. Diéguez M, Claver C, Masdeu-Bultó AM, Ruiz A, van Leeuwen PWNM, Schoemaker GC (1999) Organometallics 18:2107

    Article  Google Scholar 

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Acknowledgments

This work was supported by FONACIT (S1-2002000260) and CDCH-UCV (PG. 03-00-6928-2007). The authors are gratefully to CYTED: Red V-D and Project V-9, and Ministerio de Educación y Ciencia (MEC/FEDER) Project CTQ2006-03973/BQU.

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Authors and Affiliations

  1. Centro de Equilibrios en Solución, Escuela de Química, Facultad de Ciencias, Universidad Central de Venezuela, Caracas, Venezuela

    Rafael Vargas, Angel B. Rivas, José D. Suárez, Itzel Chaparros, Marisol C. Ortega & Alvaro J. Pardey

  2. Centro de Investigación y Desarrollo de Radiofármacos, Facultad de Farmacia, Universidad Central de Venezuela, Caracas, Venezuela

    Clementina Longo

  3. Departamento de Química Inorgánica, Instituto Universitario de Catálisis Homogénea, Instituto de Ciencia de Materiales de Aragón, Universidad de Zaragoza-C.S.I.C., 50009, Zaragoza, Spain

    Jesús J. Pérez-Torrente & Luis A. Oro

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  1. Rafael Vargas
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  2. Angel B. Rivas
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  5. Marisol C. Ortega
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  6. Alvaro J. Pardey
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  7. Clementina Longo
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Correspondence to Alvaro J. Pardey.

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Vargas, R., Rivas, A.B., Suárez, J.D. et al. Hydroformylation of Hex-1-ene by a Dinuclear gem-Dithiolato-bridged Rhodium Catalyst Under CO/H2O Conditions. Catal Lett 130, 470–475 (2009). https://doi.org/10.1007/s10562-009-9930-1

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