DAYAN ET AL.
9 of 10
[4] C. Li, Catal. Rev. Sci. Eng. 2004, 46, 419.
catalytic activities for the TH of aromatic aldehydes to benzyl
alcohols. Catalyst 2d was very effective in the TH of aromatic
aldehydes under optimized conditions (S:C = 1000:1). The
highest measured TOFs were 6000 h−1 for complexes 2a
and 2d in the TH of 4‐chlorobenzaldehyde for 10 min, at an
S:C molar ratio of 1000:1 with 2‐propanol–KOH medium
at 80 °C. It is worth noting that compounds 2a–d are tolerant
to substrate variations. Complete conversions were obtained
for the TH of ketones and aldehydes within 10–180 min.
Herein, as outlined, the catalytic systems for ketones or alde-
[5] C. Baleizão, H. Garcia, Chem. Rev. 2006, 106, 3987.
[6] C. Li, H. Zhang, D. Jiang, Q. Yang, Chem. Commun. 2007, 547.
[7] J. M. Thomas, R. Raja, Acc. Chem. Res. 2008, 41, 708.
[8] I. Domínguez, V. Fornés, M. J. Sabater, J. Catal. 2004, 228, 92.
[9] P. N. Liu, P. M. Gu, F. Wang, Y. Q. Tu, Org. Lett. 2004, 6, 169.
[10] D. M. Jiang, J. S. Gao, Q. H. Yang, J. Yang, C. Li, Chem. Mater. 2006, 18,
6012.
[11] H. Q. Yang, L. Zhang, L. Zhong, Q. H. Yang, C. Li, Angew. Chem. Int. Ed.
2007, 46, 6861.
[12] S. Y. Bai, H. Q. Yang, P. Wang, J. S. Gao, B. Li, Q. H. Yang, C. Li, Chem.
Commun. 2010, 46, 8145.
hydes were investigated with effective homogeneous (2a–d
)
and heterogeneous (3a–d) catalysts.
[13] M. Heitbaum, F. Glorius, I. Escher, Angew. Chem. Int. Ed. 2006, 45, 4732.
[14] L. Mercier, T. J. Pinnavaia, Adv. Mater. 1997, 9, 500.
Herein, an intriguing aspect of the catalytic experiments
is that the catalyst efficiency depends not only on the ligand
but also on the substrates. Electron‐withdrawing groups
introduced at the para position of acetophenones and aro-
matic aldehydes accelerate the conversion, while electron‐
donating groups slow it down. In the same way, the presence
of electron‐withdrawing groups on the phenylenediamine
ring has a beneficial effect. Interestingly, the catalytic activity
obtained for aromatic aldehydes was higher compared to that
for the TH of acetophenones. It is likely that the catalytic
activities are increased due to absence of steric hindrance in
the TH of aldehydes.
[15] D. S. Shepard, W. Zhou, T. Maschmeyer, J. M. Matters, C. L. Roper,
S. Parsons, B. F. G. Johnson, M. J. Duer, Angew. Chem. Int. Ed. 1998,
37, 2719.
[16] K. Moller, T. Bein, R. X. Fischer, Chem. Mater. 1999, 11, 665.
[17] F. Babonneau, L. Leite, S. Fontlupt, J. Mater. Chem. 1999, 9, 175.
[18] A. Szadkowska, K. Zukowska, A. E. Pazio, K. Wozniak, R. Kadyrov,
K. Grela, Organometallics 2011, 30, 1130.
[19] W. Jin, X. C. Li, B. S. Wan, J Org. Chem. 2011, 76, 484.
[20] H. S. Zhang, R. H. Jin, H. Yao, S. Tang, J. L. Zhuang, G. H. Liu, H. X. Li,
Chem. Commun. 2012, 48, 7874.
[21] Y. Q. Sun, G. H. Liu, H. Y. Gu, T. Z. Huang, Y. L. Zhang, H. X. Li, Chem.
Commun. 2011, 47, 2583.
[22] D. Singh, J. Tian, K. Mamtani, J. King, Jeffrey T. Miller, U. S. Ozkan,
Journal of Catalysis 2014, 317, 30–43.
4
| CONCLUSIONS
[23] C. Janke, M. S. Duyar, M. Hoskins, R. Farrauto, Appl. Catal. B 2014,
152–153, 184.
Herein, we have reported the fabrication and characterization
of complexes 2a–d for homogeneous catalysis and materials
3a–d for heterogeneous catalysis containing various
phenylendiamine and sulfonamide fragments. The catalytic
activities of all the complexes and materials were tested and
showed high catalytic activity in the TH of acetophenones
and aromatic aldehydes, the findings being comparable to
the homogeneous catalysis results. Although the best cataly-
sis results were found with the homogeneous catalyst 2d,
the performance of 3a material was higher compared to the
homogeneous catalyst. When the catalytic data are summa-
rized, the catalytic efficiency for the TH of acetophenones
and aldehydes increases in the order 2c < 2b < 2a < 2d for
the complexes and in the order 3c < 3b < 3a < 3d for the
materials. Consequently, it is clear that the Ru(II) complexes
and their materials (2a–d, 3a–d) investigated herein show good
efficiency in TH reactions compared to analogues.[42–51]
[24] J. Jae, W. Zheng, A. M. Karim, W. Guo, R. F. Lobo, D. G. Vlachos,
ChemCatChem 2014, 6, 848.
[25] J. Li, L. Ackermann, Tetrahedron 2014, 70, 3342.
[26] C. Chen, S. H. Hong, Org. Lett. 2012, 14, 2992.
[27] B. Barati, M. Moghadam, A. Rahmati, V. Mirkhani, S. Tangestaninejad,
I. Mohammadpoor‐Baltork, J. Organometal. Chem. 2013, 724, 32.
[28] B. Chatterjee, C. Gunanathan, Chem. Commun. 2014, 50, 888.
[29] S. Dayan, A. Çetin, N. B. Arslan, N. Kalaycioglu Ozpozan, N. Ozdemir,
O. Dayan, Polyhedron 2015, 85, 748.
[30] S. Liu, J. Zhang, W. Tu, J. Bao, Z. Dai, Nanoscale 2014, 6, 2419.
[31] K. Neuthe, F. Bittner, F. Stiemke, B. Ziem, J. Du, M. Zellner, M. Wark,
T. Schubert, R. Haag, Dyes Pigm. 2014, 104, 24.
[32] G. Tamasi, C. Bernini, G. Corbini, N. F. Owens, L. Messori, F. Scaletti,
L. Massai, P. L. Giudice, R. Cini, J. Inorg. Biochem. 2014, 134, 25.
[33] S. S. Braga, J. Marques, E. Heister, C. V. Diogo, P. J. Oliveira, F. A. A. Paz,
T. M. Santos, M. Paula, M. Marques, BioMetals 2014, 27, 507.
[34] E. Lebon, R. Sylvain, R. E. Piau, C. Lanthony, J. Pilmé, P. Sutra, M. Boggio‐
Pasqua, J. L. Heully, F. Alary, A. Juris, A. Igau, Inorg. Chem. 2014, 53,
1946.
[35] H. Liu, S. Liang, W. Wang, T. Jiang, B. Han, J. Mol. Catal. A 2011, 341, 35.
ACKNOWLEDGEMENT
[36] Y. Yang, Z. Weng, S. Muratsugu, N. Ishiguro, S. Ohkoshi, M. Tada,
We acknowledge the financial support by TUBITAK
(ARDEB) (113Z505).
Chem. – Eur. J. 2012, 18, 1142.
[37] S. A. da S. Corradini, G. G. Lenzi, M. K. Lenzi, C. M. F. Soares, O. A. A.
Santos, J. Non‐Cryst. Solids 2008, 354, 4865.
[38] E. Castillejos, M. Jahjah, I. Favier, A. Orej, C. Pradel, E. Teuma, A. M.
REFERENCES
Masdeu‐Bult, P. Serp, M. Gómeza, ChemCatChem 2012, 4, 118.
[1] C. E. Song, S. G. Lee, Chem. Rev. 2002, 102, 3495.
[2] Q. H. Fan, Y. M. Li, A. S. C. Chan, Chem. Rev. 2002, 102, 3385.
[39] L. Lou, H. Dua, Y. Shen, K. Yu, W. Yu, Q. Chen, S. Liu, Micropor. Mesopor.
Mater. 2014, 187, 94.
[3] Q. H. Xia, H. Q. Ge, C. P. Ye, Z. M. Liu, K. X. Su, Chem. Rev. 2005, 105,
[40] J. Long, G. Liu, T. Cheng, H. Yao, Q. Qian, J. Zhuang, F. Gao, H. Li,
1603.
J. Catal. 2013, 298, 41.