50
Z.D. Petrovi´c et al. / Journal of Molecular Catalysis A: Chemical 327 (2010) 45–50
implying again that the acetic acid leaves the reaction system. In
this way the trans-[PdCl2(DEA)2] complex is yielded.
[15] D. Zhao, Z.F. Fei, T.J. Geldbach, R. Scopelliti, P.J. Dyson, J. Am. Chem. Soc. 126
(2004) 15876–15882.
[16] Z.F. Fei, D. Zhao, D. Pieraccini, W.H. Ang, T.J. Geldbach, R. Scopelliti, C. Chiappe,
P.J. Dyson, Organometallics 26 (2007) 1588–1598.
[17] A.J. Carmichael, M.J. Earle, J.D. Holbrey, P.B. McCormac, K.R. Seddon, Org. Lett.
1 (1999) 997–1000.
[18] S. Keskin, D. Kayrak-Talay, U. Akman, Ö. Hortac¸ su, J. Supercrit. Fluids 43 (2007)
150–180.
It is worth noting that the activation energy for the formation
In a similar way, the activation energy for the formation of TS2
was calculated as a difference between the free energy of TS2 and
the structure obtained by optimizing 1 and 7 together (8 and 9 in
Fig. 3 of Supplementary Data). We suppose that the activation bar-
rier for the formation of TS2 is higher than that for the formation of
TS1 because of numerous hydrogen bonds in the structure 9. Rel-
atively high calculated activation energies can be attributed to the
fact that the calculations were performed in vacuum. We assume
that in practice, in the presence of the solvent, the activation bar-
riers are lowered.
[19] J. Gorman, Sci. News 160 (2001) 156–158.
[20] J.F. Brennecke, E.J. Maginn, AIChE J. 47 (2001) 2384–2388.
[21] Q. Yang, D.D. Dionysiou, J. Photochem. Photobiol. A: Chem. 165 (2004) 229–240.
[22] K.R. Seddon, Kinet. Catal. 37 (1996) 693–697.
ˇ
[23] C. Lagrost, D. Carriei, M. Vaultier, P. Hapiot, J. Phys. Chem. A 107 (2003) 745–752.
[24] A. Shariati, C.J. Peters, J. Supercrit. Fluids 34 (2005) 171–176.
[25] A. Shariati, K. Gutkowski, C.J. Peters, AIChE J. 51 (2005) 1532–1540.
[26] H. Zhao, S. Xia, P. Ma, J. Chem. Technol. Biotechnol. 80 (2005) 1089–1096.
[27] D.E. Kaufmann, M. Nouroozian, H. Henze, Synlett 11 (1996) 1091–1092.
[28] W.K. Kottsieper, O. Stelzer, P. Wasserscheid, J. Mol. Catal. A: Chem. 175 (2001)
285–288.
[29] D. Zhao, Z. Fei, R. Scopelliti, P. Dyson, J. Inorg. Chem. 43 (2004) 2197–2205.
[30] N. Audic, H. Clavéier, M. Mauduit, C.J. Guillemin, J. Am. Chem. Soc. 125 (2003)
9248–9249.
4. Conclusion
[31] J.D. Brauer, K. Kottsieper, C. Liek, O. Stelzer, H. Waffenschmidt, P. Wasserscheid,
J. Organomet. Chem. 630 (2001) 177–184.
It was found that the reaction of PdCl2 with diethanolamine
and N,N-diethylethanolamine ionic liquids provides the ionic
liquid–palladium catalytic systems for green Heck reaction. Our
DFT investigation presented herein provides mechanistic insight
into the formation of the trans-[PdCl2(DEA)2] complex that acts
as a precatalyst. The used ILs facilitate solubility of the Pd(II)
precatalysts, increase catalyst stability during the reaction, and
function as reaction media, bases, precatalyst-precursors, good
coordinating ligands, and mobile support for active Pd species.
Thus, Heck reaction occurs without additional solvents, ligands and
bases, that makes experimental procedure much simpler. This used
IL–Pd catalytic system is ecological friendly and can be recovered
and recycled what make it attractive and economically accept-
able.
[32] C.C. Brasse, U. Englert, A. Salzer, H. Waffenschmidt, P. Wasserscheid,
Organometallics 19 (2000) 3818–3823.
[33] P. Wasserscheid, H. Waffenschmidt, P. Machnitzki, W.K. Kottsieper, O. Stelzer,
Chem. Commun. (2001) 451–452.
[34] F. Favre, H. Olivier-Bourbigou, D. Commereuc, L. Saussine, Chem. Commun.
(2001) 1360–1361.
[35] E.A. Visser, P.R. Swatloski, M.W. Reichert, H.J. Davis Jr., D.R. Rogers, R. Mayton,
S. Sheff, A. Wierzbicki, Chem. Commun. (2001) 135–136.
[36] E.A. Visser, P.R. Swatloski, M.W. Reichert, R. Mayton, S. Sheff, A. Wierzbicki, H.J.
Davis Jr., D.R. Rogers, Environ. Sci. Technol 36 (2002) 2523–2529.
[37] D.E. Bates, D.R. Mayton, I. Ntai, H.J. Davis Jr., J. Am. Chem. Soc. 124 (2002)
926–927.
[38] M.K. Lee, T.Y. Lee, B.J.I. Lin, J. Mater. Chem. 13 (2003) 1079–1084.
[39] M.J. Frisch, W.G. Trucks, B.H. Schlegel, E.G. Scuseria, A.M. Robb, R.J. Cheeseman,
G.V. Zakrzewski, A.J. Montgomery Jr., E.R. Stratmann, C.J. Burant, S. Dapprich,
M.J. Millam, D.A. Daniels, N.K. Kudin, C.M. Strain, O. Farkas, J. Tomasi, V. Barone,
M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski,
A.G. Petersson, Y.P. Ayala, Q. Cui, K. Morokuma, D.A. Malick, D.K. Rabuck, K.
Raghavachari, B.J. Foresman, J. Cioslowski, V.J. Ortiz, G.A. Baboul, B.B. Stefanov,
G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, L.R. Martin, J.D. Fox, T.
Keith, A.M. Al-Laham, Y.C. Peng, A. Nanayakkara, M. Challacombe, P.M.W. Gill,
B. Johnson, W. Chen, W.M. Wong, L.J. Andres, C. Gonzalez, M. Head-Gordon, S.E.
Replogle, A.J. Pople, Gaussian 03, Revision E. 01-SMP, Gaussian Inc., Pittsburgh,
PA, 2003.
Acknowledgements
This work is supported by the Ministry of Science and Environ-
ment of Serbia, Project Nos. 142013 B and 142025.
[40] D.A. Becke, Phys. Rev. A 38 (1988) 3098–3100.
[41] C. Lee, W. Yang, R.G. Parr, Phys. Rev. B 37 (1988) 785–789.
[42] D.A. Becke, J. Chem. Phys. 98 (1993) 5648–5652.
[43] J.P. Hay, R.W. Wadt, J. Chem. Phys. 82 (1985) 270–283.
[44] Z.D. Petrovic´, S. Markovic´, D. Simijonovic´, V. Petrovic´, Monatsh. Chem. 140
(2009) 371–374.
[45] S. Markovic´, Z.D. Petrovic´, V. Petrovic´, Monatsh. Chem. 140 (2009) 171–175.
[46] P.V. Bohm, A.W. Herrmann, Chem. Eur. J. 6 (2000) 1017–1025.
[47] L. Xu, W. Chen, J. Ross, J. Xiao, Org. Lett. 3 (2001) 295–297.
[48] K. Selvakumar, A. Zapf, M. Beller, Org. Lett. 4 (2002) 3031–3033.
[49] A.S.K. Vallin, P. Emilsson, M. Larhed, A. Hallberg, J. Org. Chem. 67 (2002)
6243–6246.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
References
[1] F.R. Heck, Acc. Chem. Res. 12 (1979) 146–151.
[2] F.R. Heck, Palladium Reagents in Organic Synthesis, Academic, London, UK,
1985.
[50] (a) B.S. Park, H. Alper, Org. Lett. 5 (2003) 3209–3212;
(b) V. Calo, A. Nacci, A. Monopoli, L. Lorez, A. di Cosmo, Tetrahedron 57 (2001)
6071–6077.
[51] (a) B. Gianfranco, C. Sandro, F. Giancarlo, Synlett 3 (2002) 439–442;
(b) J. Sillberg, T. Schareina, R. Kempe, K. Wurst, R.M. Buchmeiser, J. Organomet.
Chem. 622 (2001) 6–18.
[52] X. Xie, B. Chen, J. Lu, J. Han, X. She, X. Pan, Tetrahedron Lett. 45 (2004)
6235–6237.
[53] Z.D. Petrovic´, M.I. Djuran, F.W. Heinemann, S. Rajkovic´, S.R. Trifunovic´, Bioorg.
[3] F.R. Heck, in: M.B. Trost, I. Flemming (Eds.), Comprehensive Organic Synthesis,
vol. 4, Pergamon, New York, NY, 1991 (Chapter 4.3).
[4] B. Cornils, A.W. Herrmann, Applied Homogeneous Catalysis with Organometal-
lic Compounds, Comprehensive Handbook in Two Volumes, VCH, Weinheim,
New York, NY, 1996.
[5] E. Negishi, Handbook of Organopalladium Chemistry for Organic Synthesis,
Wiley-Interscience, New York, NY, 2002.
[6] A. Meijere, F. Diederich, Metal-catalyzed Cross-coupling Reactions, Wiley-VCH,
New York, NY, 2004.
[7] J. Dupont, R.F. de Souza, P.A.Z. Suarez, Chem. Rev. 102 (2002) 3667.
[8] J.L. Anderson, R. Ding, A. Ellern, D.W. Armstrong, J. Am. Chem. Soc. 127 (2005)
593–604.
Chem. 34 (2006) 225–234.
[54] S. Bräse, A. de, Meijere, in: F. Diederich, J.P. Stang (Eds.), Metal-catalyzed Cross-
coupling Reactions, Wiley-VCH, Chichester, 1998.
[55] J. Tsuji, Palladium Reagents and Catalysts-innovations in Organic Synthesis,
Wiley, Chichester, 1995.
[9] V. Calò, A. Nacci, A. Monopoli, Eur. J. Org. Chem. 2006 (2006) 3791–3802.
[10] C.C. Cassol, A.P. Umpierre, G. Machado, S.I. Wolke, J. Dupont, J. Am. Chem. Soc.
127 (2005) 3298–3299.
[11] J. Mo, L. Xu, J. Xiao, J. Am. Chem. Soc. 127 (2005) 751–760.
[12] J.C. Xiao, B. Twamley, J.M. Shreeve, Org. Lett. 6 (2004) 3845–3847.
[13] V. Calò, A. Nacci, A. Monopoli, A. Detomaso, P. Iliade, Organometallics 22 (2003)
4193–4197.
[56] T. Jeffery, Tetrahedron Lett. 26 (1985) 2667–2670.
[57] C. Amatore, M. Azzabi, A. Jutand, J. Am. Chem. Soc. 113 (1991) 8375–8384.
[58] C. Ye, J.C. Xiao, B. Twamley, A.D. LaLonde, M.G. Norton, J.M. Shreeve, Eur. J. Org.
Chem. (2007) 5095–5100.
[59] A.J. Arduengo III, R. Krafczyk, R. Schmutzler, H.A. Craig, J.R. Goerlich, W.J. Mar-
shall, M. Unverzagt, Tetrahedron 55 (1999) 14523–14534.
[60] Z.D. Petrovic´, V.P. Petrovic´, D. Simijonovic´, S. Markovic´, J. Organomet. Chem.
694 (2009) 3852–3858.
[14] G.S. Fonseca, A.P. Umpierre, P.F. Fichtner, S.R. Teixeira, J. Dupont, Chem. Eur. J.
9 (2003) 3263–3269.