2166
S. Karabulut et al. / Journal of Organometallic Chemistry 695 (2010) 2161e2166
Merck and used as received. The ligand (IPr: 1,3-bis(2,6-diisopro-
pylphenyl)-1,3-dihydro-2H-imidazol-2-ylidene) and the Ru
complex Ru]CHPhCl2(PCy3)(IPr) were synthesised according to
previous literature methods [41e43].
References
[1] P. Aschwanden, E.M. Carreira, Addition of terminal acetylides to C]O and C]
N electrophiles. in: F. Diederich, P.J. Stang, R.R. Tykwinski (Eds.), Acetylene
Chemistry-Chemistry, Biology and Materials Science. Wiley-VCH, Weinheim,
2005, pp. 101e138.
[2] M. Beller, J. Seayad, A. Tillack, H. Jiao, Angew. Chem. Int. Ed. 43 (2004)
3368e3398.
4.2. Instrumentation
[3] E. Negishi, L. Anastasia, Chem. Rev. 103 (2003) 1979e2018.
[4] J.A. Varela, C. Saa, Chem. Rev. 103 (2003) 3787e3802.
[5] D.R. Kanis, M.A. Ratner, T.J. Marks, Chem. Rev. 94 (1994) 195e242.
[6] M. Nishiura, Z. Hou, J. Mol. Catal. A: Chem. 213 (2004) 101e106.
[7] M. Ueda, I. Tomita, Polym. Bull. 51 (2004) 359e364.
[8] C.K. Choi, I. Tomita, T. Endo, Macromolecules 33 (2004) 1487e1488.
[9] T. Mitsudo, Y. Hori, Y. Watanabe, J. Org. Chem. 50 (1985) 1566e1568.
[10] C. Ruppin, P. Dixneuf, Tetrahedron Lett. 27 (1986) 6323e6324.
[11] Z. Kabouche, C. Bruneau, P. Dixneuf, J. Chem. Soc. Perkin Trans. 1 (1991)
1197e1201.
[12] V. Cadierno, J. Francos, J. Gimeno, Green Chem. 12 (2010) 135e143.
[13] P. Dixneuf, C. Bruneau, S. Derien, Pure Appl. Chem. 70 (1998) 1065e1071.
[14] H. House, D. Crumrine, A. Teranishi, H. Olmstead, J. Am. Chem. Soc. 95 (1973)
3310e3324.
[15] B. Trost, G. Kottirsc, J. Am. Chem. Soc. 112 (1990) 2816e2818.
[16] L. Meriwether, E. Colthup, G. Kennerly, J. Org. Chem. 26 (1961) 5163e5169.
[17] M. Akita, H. Yasuda, A. Nakamura, Bull. Chem. Soc. Jpn. 57 (1984) 480e487.
[18] C. Banchini, P. Frediani, D. Masi, M. Peruzzini, F. Zanobini, Organometallics 13
(1994) 4616e4632.
1H NMR and 31P NMR spectra were recorded at 25 ꢀC with
a Bruker GmbH 400 MHz high performance digital FT NMR spec-
trometer using CDCl3 as solvent. Tetramethylsilane was used for the
1H NMR reference and H3PO4 for the 31P NMR reference. GC-MS
analyses were performed with a Shimadzu GCMSQP5050A using an
Optima column-5, 1.0
m
m (50 m ꢁ 0.32 mm), and a temperature
range of 50e300 ꢀC (15 ꢀC/min). The carrier gas was helium with an
elution rate of 1 mL/min.
4.3. General procedure for carboxylic acid addition reactions
The alkyne (0.58 mmol) and 4 mol equivalents of the acid (2.29
mmol) were added to a pre-heated reactor. After addition of Ru-
catalyst (0.02 g, 0.023 mmol), the reaction mixture was stirred at 65
ꢀC under an atmosphere of nitrogen. In order to determine the yield
and product distributions, small samples were periodically drawn
out from the solution and analysed by the GC-MS. The structural
identifications were carried out by 1H NMR analysis on samples
withdrawn from the reaction mixtures at maximum yield.
[19] C. Yi, N. Liu, Organometallics 17 (1998) 3158e3160.
[20] C.S. Yi, R. Gao, Organometallics 28 (2009) 6585e6592.
[21] C. Bruneau, P. Dixneuf, J. Chem. Soc. Chem. Commun. 6 (1997) 507e513.
[22] C. Bruneau, P. Dixneuf, Acc. Chem. Res. 32 (1999) 311e323.
[23] V. Dragutan, I. Dragutan, L. Delaude, A. Demonceau, Coord. Chem. Rev. 251
(2007) 765e794.
[24] K. Melis, P. Samulkiewicz, J. Rynkowski, F. Verpoort, Tetrahedron Lett. 43
(2002) 2713e2716.
[25] T. Opstal, F. Verpoort, Synlett 6 (2002) 935e942.
[26] X. Chen, P. Xue, H.H.Y. Sung, I.D. Williams, M. Peruzzini, C. Bianchini, G. Jia,
Organometallics 24 (2005) 4330e4332.
4.4. General procedure for homodimerisation reactions
[27] B. Clercq, F. Verpoort, J. Organomet. Chem. 672 (2003) 11e16.
[28] C. Yi, N. Liu, A.L. Rheingold, L.M. Liable-Sands, Organometallics 16 (1997)
3910e3913.
[29] Q. Willem, F. Nicks, X. Sauvage, L. Delaude, A. Demonceau, J. Organomet.
Chem. 694 (2009) 4049e4055.
The Ru-catalyst (0.02 g, 0.023 mmol) and the terminal alkyne
(0.58 mmol) were added to a pre-heated reactor. The reaction
mixture was stirred at 65 ꢀC under an atmosphere of nitrogen. In
order to determine the yield and product distributions, small
samples were periodically drawn out from the solution and ana-
lysed by the GC-MS. The structural identifications were carried out
by 1H NMR analysis on samples withdrawn from the reaction
mixtures at maximum yield.
[30] F. Nicks, R. Aznar, D. Sainz, G. Muller, A. Demonceau, Eur. J. Org. Chem. 29
(2009) 5020e5027.
[31] J. Tripathy, M. Bhattacharjee, Tetrahedron Lett. 50 (2009) 4863e4865.
[32] K. Melis, F. Verpoort, J. Mol. Catal. A: Chem. 194 (2003) 39e47.
[33] K. Melis, T. Opstal, F. Verpoort, Eur. Org. Chem. 22 (2002) 3779e3784.
[34] M. Shimizu, K. Hirano, T. Satoh, M. Miura, J. Org. Chem. 74 (2009) 3478e3483.
[35] K. Ueura, T. Sato, M. Miura, Org. Lett. 9 (2007) 1407e1409.
[36] H. Nakagawa, Y. Okimoto, S. Sakaguchi, Y. Ishii, Tetrahedron Lett. 44 (2003)
103e106.
Acknowledgments
[37] K. Melis, D. Vos, P. Jacobs, F. Verpoort, J. Organomet. Chem. 671 (2003)
131e136.
[38] M. Katayama, T. Nakayama, C. Nakano, K. Wada, Akamatsu, F. Ozawa,
Macromolecules 37 (2004) 13e17.
[39] J. Oshita, K. Furumori, A. Matsuguchi, M. Ishikawa, J. Org. Chem. 55 (1990)
3277e3280.
[40] Y. Gao, R.J. Puddephatt, Inorg. Chim. Acta 350 (2003) 101e106.
[41] W. Baratta, W.A. Herrmann, P. Rigo, J. Schwarz, J. Organomet. Chem. 593
(2000) 489e493.
[42] A.J. Arduengo, R. Krafczyk, R. Schmutzler, Tetrahedron 55 (1999)
14523e14534.
The authors are indebted to the Scientific and Technological
Research Council of Turkey (TUBITAK, 107T084) and Hacettepe
University (0801601008) for a research grant.
Appendix. Supplementary data
Supplementary data associated with this article can be found in
[43] A. Fürstner, L. Ackermann, B. Gabor, R. Goddard, C.W. Lehmann, R. Mynott,
F. Stelzer, O.R. Thiel, Chem. Eur. J. 7 (2001) 3236e3253.