242
C.-S. Lee et al. / Journal of Organometallic Chemistry 724 (2013) 235e243
H
¼ 1.8 Hz, 4H, imi-H), 6.41 (d, JHeH ¼ 13.8 Hz, 2H, NCH
N), 3.77 (t, JHeH ¼ 6.6 Hz, 8H, NCH
.34 (t, JHeH ¼ 6.3 Hz, 8H, BrCH CH ), 1.77 (m, 8H, NCH CH
) ppm; C NMR (CD CN): 138.0 (imi-C), 123.6
imi-C), 122.8 (imi-C), 58.9 (NCH N), 49.0 (NCH CH ), 34.5
BrCH CH2), 29.2 (NCH CH ), 28.5 (BrCH
2
N), 6.22 (d,
CH ),
), 1.67
References
J
3
HeH ¼ 13.8 Hz, 2H, NCH
2
2
2
[1] (a) J.-C. Xiao, B. Twamley, J.M. Shreeve, Org. Lett. 6 (2004) 3845e3847;
2
2
2
2
(
(
b) Y. Morisaki, T. Ishida, Y. Chujo, Org. Lett. 8 (2006) 1029e1032;
c) M.S. Yoon, D. Ryu, J. Kim, K.H. Ahn, Organometallics 25 (2006) 2409e2411;
1
3
(
(
(
m, 8H, BrCH
2
CH
2
3
d
2
2
2
(d) Q. Yao, E.P. Kinney, C. Zheng, Org. Lett. 6 (2004) 2997e2999;
e) A. Deagostino, C. Prandi, P. Venturello, Org. Lett. 5 (2003) 3815e3817;
(f) J.D. Crowley, K.D. Hanni, A.-L. Lee, D.A. Leigh, J. Am. Chem. Soc. 129 (2007)
2092e12093;
(g) X. Zhang, Z. Xi, A. Liu, W. Chen, Organometallics 27 (2008) 4401e4406;
h) W.H. Yang, C.S. Lee, S. Pal, Y.N. Chen, W.S. Hwang, I.J.B. Lin, J.C. Wang,
(
2
2
2
2
CH
2
) ppm. Mass (MALDI):
þ
2þ
m/z ¼ 1083.26 [M þ PF
6
] , 419.32 [M] . Anal. Calcd. for
C H44Br F N P Pd: C 29.31, N 9.12, H 3.58. Found: C 29.25, N 9.09,
30 4 12 8 2
1
(
H3.72.
J. Organomet. Chem. 693 (2008) 3729e3740.
[2] (a) I.P. Beletskaya, A.V. Cheplakov, Chem. Rev. 100 (2000) 3009e3066;
(
(
(
(
(
(
b) J.A. Mata, M. Poyatos, E. Peris, Coord. Chem. Rev. 251 (2007) 841e859;
c) M. Poyatos, J.A. Mata, E. Peris, Chem. Rev. 109 (2009) 3677e3707;
d) L. Liu, F. Wang, M. Shi, Eur. J. Inorg. Chem. (2009) 1723e1728;
e) R. Corberán, E. Mas-Marzá, E. Peris, Eur. J. Inorg. Chem. (2009) 1700e1716;
f) M.C. Jahnke, T. Pape, F.E. Hahn, Eur. J. Inorg. Chem. (2009) 1960e1969;
g) S. Díez-Gonzílez, N. Marion, S.P. Nolan, Chem. Rev. 109 (2009) 3612e3672;
4
.4. General procedure for the Heck reaction
A mixture of Pd(II) catalyst (1.2 mol%), NaOAc (2 mmol), aryl
bromide (1 mmol), styrene (1.5 mmol), and DMF (2.5 mL) was
charged in a vial under air, locked up with a screw cap and then
heated at 140 C in an oil bath. After the completion of the reaction,
(h) R.H. Crabtree, Chem. Rev. 112 (2012) 1536e1554.
[3] (a) A.F. Littke, G.C. Fu, Angew. Chem. Int. Ed. 41 (2002) 4176e4211;
ꢀ
(
(
b) U. Christmann, R. Vilar, Angew. Chem. Int. Ed. 44 (2005) 366e374;
c) A. Zapf, M. Beller, Chem. Commun. (2005) 431e440;
the mixture was extracted with diethyl ether or dichloromethane/
H
2
O (3 mL/2 mL) four times. The organic phase was separated and
(d) S. Díez-González, S.P. Nolan, Top. Organomet. Chem. 21 (2007) 47e82;
e) N. Iranpoor, H. Firouzabadi, S. Motevalli, M. Talebi, J. Organomet. Chem.
08 (2012) 118e124;
f) E. Negishi, Handbook of Organopalladium Chemistry for Organic Synthesis,
vol. 1, Wiley, New York, 2002, p. 1209;
g) M. Beller, C. Bolm, Transition Metals for Organic Synthesis, second ed., vol.
1, Wiley, New York, 2004, p. 271;
(
7
(
dried in vacuo. The crude product was purified by column chro-
matography (silica gel) using 5:1 n-hexane:EA (V/V).
(
4.5. General procedure for the recycling experiment
(
(
h) G.C. FU, Acc. Chem. Res. 41 (2008) 1555e1564;
i) D. Pandiarajan, R. Ramesh, J. Organomet. Chem. 708e709 (2012) 18e24.
The reusability of Pd(II) catalyst for Heck reaction was examined
[
4] (a) C. Zhang, J. Huang, M.L. Trudell, S.P. Nolan, J. Org. Chem. 64 (1999) 3804e3805;
(b) M.S. Viciu, R.M. Kissling, E.D. Stevens, S.P. Nolan, Org. Lett. 4 (2002) 2229e
following a strategy of a repetitive process described in the litera-
ture [22]. Originally, the reaction was carried out with 1 mmol aryl
bromide, 1.5 mmol styrene, 2 mmol NaOAc, and 1.2 mol% Pd(II)
2
(
6
231;
c) J. Schutz, E. Herdtweck, W.A. Herrmann, Organometallics 23 (2004) 6084e
086;
(d) J.R. Miecznikowski, R.H. Crabtree, Organometallics 23 (2004) 629e631;
e) M.S. Viciu, E.D. Stevens, J.L. Petersen, S.P. Nolan, Organometallics 23 (2004)
752e3755.
ꢀ
catalyst in 2.5 mL DMF at 140 C for desired time. On completion of
(
3
the reaction, the reaction mixture was cooled. After the product
was extracted from the reaction mixture as described in Section 4.4,
the water layer was decanted and the residue was dried in vacuo
before next cycle. The same amount of aryl bromide, styrene, DMF,
and NaOAc were added as in the original reaction, and the reaction
was continued for the next run.
[
5] (a) W.A. Herrmann, M. Elison, J. Fischer, C. Köcher, G.R.J. Artus, Angew. Chem.
Int. Ed. 34 (1995) 2371e2374;
(
(
b) E. Peris, J.A. Loch, J. Mata, R.H. Crabtree, Chem. Commun. (2001) 201e202;
c) S. Gründemann, M. Albrecht, J.A. Loch, J.W. Faller, R.H. Crabtree, Organo-
metallics 20 (2001) 5485e5488;
(d) V. Cesar, S. Bellemin-Loponnaz, L.H. Gade, Organometallics 21 (2002)
5204e5208;
(
(
e) A.W. Waltman, R.H. Grubbs, Organometallics 23 (2004) 3105e3107;
f) A.O. Larsen, W. Leu, C.N. Oberhuber, J.E. Campbell, A.H. Hoveyda, J. Am.
4
.6. X-ray crystallography
Chem. Soc. 126 (2004) 11130e11131;
g) Y.A. Wanniarachchi, M.A. Khan, L.M. Slaughter, Organometallics 23 (2004)
(
Single crystals of [Ag
2
(
PyBuCCme
)
2
](PF
6
)
6
(5), [Pd
2
(PyBuCCme
)
2
5881e5884;
BrBu
me
(h) D.J. Nielsen, K.J. Cavell, B.W. Skelton, A.H. White, Organometallics 25
Cl
](PF )
2 6 6
(6), and [Pd(
CC
2 6 2
) ](PF ) (8) suitable for X-ray diffrac-
(2006) 4850e4856.
tion were mounted on the tips of glass fibers with epoxy resin and
subjected to X-ray diffraction analysis. Datawere collected on a Bruker
APEX II diffractometer, using graphite monochromated Mo Ka radia-
tion (
which corrects for Lorentz and polarization effects. Absorption
corrections were performed using multiscan (SADABS). Structures
were solved by the use of direct methods, and refinement was per-
formed by the least-squares methods on F with the SHELXL-97
package [25]. All H atoms were added in idealized positions. Details
of data are tabulated in Table 4.
[
[
[
6] C.S. Lee, S. Pal, W.S. Yang, W.S. Hwang, I.J.B. Lin, J. Mol. Catal. A Chem. 280
(2008) 115e121.
7] C. Tubaro, A. Biffis, C. Ganzato, M. Zecca, M. Basato, J. Mol. Catal. A Chem. 248
(
2005) 93e98.
ꢀ
l
¼ 0.71073 A) [24]. Data reduction was performed with SAINT,
8] (a) B. Cornils, E.G. Kuntz, J. Organomet. Chem. 502 (1995) 177e186;
(b) C.C. Brasse, U. Englert, A. Salzer, Organometallics 19 (2000) 3818e3823;
(
2
(
c) C.S. Consorti, G.L.P. Aydos, G. Ebeling, J. Dupont, Org. Lett. 10 (2008) 237e
40;
d) R.B. DeVasher, L.R. Moore, K.H. Shaughnessy, J. Org. Chem. 69 (2004)
2
7919e7927;
(e) R.T. Smith, M.C. Baird, Inorg. Chim. Acta 62 (1982) 135e139;
(
(
f) K.H. Shaughnessy, Chem. Rev. 109 (2009) 643e710;
g) G.F. Silbestri, J.C. Flore, E. de Jesús, Organometallics 31 (2012) 3355e3360.
[9] L.R. Moore, E.C. Western, R. Craciun, J.M. Spruell, D.A. Dixon, K.P. O’Halloran,
K.H. Shaughnessy, Organometallics 27 (2008) 576e593.
Acknowledgments
[10] D.M. Chisholm, J.S. McIndoe, Dalton Trans. (2008) 3933e3945.
[11] (a) T. Jeffery, Tetrahedron Lett. 35 (1994) 3051e3054;
(
(
b) D. Schönfelder, O. Nuyken, R. Weberskirch, J. Organomet. Chem. 690
2005) 4648e4655;
The authors acknowledge the National Science Council (Taiwan)
and National Dong Hwa University for financial support.
(c) D. Schönfelder, K. Fischer, M. Schmidt, O. Nuyken, R. Weberskirch,
Macromolecules 38 (2005) 254e262;
(d) E.A.B. Kantchev, C.J. O’Brien, M.G. Organ, Angew. Chem. Int. Ed. 46 (2007)
2
768e2813;
Appendix A. Supplementary material
(
(
e) B.H. Lipshutz, B.R. Taft, Org. Lett. 10 (2008) 1329e1332;
f) Y. Uozumi, T. Kimura, Synlett 12 (2002) 2045e2048;
CCDC 823966, 879708 and 879709 contain the supplementary
crystallographic data for this paper. These data can be obtained free
(g) S. Gülcemal, S. Kahraman, J.-C. Daran, E. Çetinkaya, B. Çetinkaya,
J. Organomet. Chem. 694 (2009) 3580e3589.
12] J.C. Garrison, W.J. Youngs, Chem. Rev. 105 (2005) 3978e4008.
13] J.C. Garrison, R.S. Simons, J.M. Talley, C. Wesdemiotis, C.A. Tessier, W.J. Youngs,
Organometallics 20 (2001) 1276e1278.
[
[