Effect of the Para-substituent of the Tridentate Pyridine-based Ru(Ⅱ) Complex upon the Catalytic Activity in Transfer Hydrogenation

Chinese Journal of Chemical Engineering ›› 2011, Vol. 19 ›› Issue (1): 169-172.

Effect of the Para-substituent of the Tridentate Pyridine-based Ru(Ⅱ) Complex upon the Catalytic Activity in Transfer Hydrogenation

杨刚, 秦冬玲, 高宏飞, 徐南平

State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing University of Technology, Nanjing 10009, China

收稿日期:2010-04-21 修回日期:2010-12-17 出版日期:2011-02-28 发布日期:2011-02-28
通讯作者: YANG Gang, E-mail: yanggang@njut.edu.cn
基金资助:
Supported by the National Natural Science Foundation of China(20576052);the Joint Innovation Fund of Jiangsu Province(BY2009107);the National Basic Research Program of China(2003CB615707)

Effect of the Para-substituent of the Tridentate Pyridine-based Ru(Ⅱ) Complex upon the Catalytic Activity in Transfer Hydrogenation

YANG Gang, QING Dongling, GAO Hongfei, XU Nanping

State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing University of Technology, Nanjing 10009, China

Received:2010-04-21 Revised:2010-12-17 Online:2011-02-28 Published:2011-02-28
Supported by:
Supported by the National Natural Science Foundation of China(20576052);the Joint Innovation Fund of Jiangsu Province(BY2009107);the National Basic Research Program of China(2003CB615707)

摘要/Abstract

摘要： Three stable 4-substituted pyridine-based ruthenium(Ⅱ)complexes[RuCl₂(PPh₃)L](L=4-R-2,6-bis (diethylaminomethylene)pyridine,R=Br,H or allyloxy)were synthesized.The catalytic activities of the complexes toward transfer hydrogenation from alcohols to ketones were investigated.The electronic effects of the para-substituent in the pyridyl ring were probed and we found that the electron-donating group increased the catalytic activity.The result suggests that an electron-donating group is probably preferential for linking the catalytic ruthenium complex and the chemically inert supporting molecules such as a carbosilane dendrimer.

关键词: ruthenium(Ⅱ)complexes, tridentate, transfer hydrogenation, catalyst

Abstract: Three stable 4-substituted pyridine-based ruthenium(Ⅱ)complexes[RuCl₂(PPh₃)L](L=4-R-2,6-bis (diethylaminomethylene)pyridine,R=Br,H or allyloxy)were synthesized.The catalytic activities of the complexes toward transfer hydrogenation from alcohols to ketones were investigated.The electronic effects of the para-substituent in the pyridyl ring were probed and we found that the electron-donating group increased the catalytic activity.The result suggests that an electron-donating group is probably preferential for linking the catalytic ruthenium complex and the chemically inert supporting molecules such as a carbosilane dendrimer.

Key words: ruthenium(Ⅱ)complexes, tridentate, transfer hydrogenation, catalyst

杨刚, 秦冬玲, 高宏飞, 徐南平. Effect of the Para-substituent of the Tridentate Pyridine-based Ru(Ⅱ) Complex upon the Catalytic Activity in Transfer Hydrogenation[J]. Chinese Journal of Chemical Engineering, 2011, 19(1): 169-172.

YANG Gang, QING Dongling, GAO Hongfei, XU Nanping. Effect of the Para-substituent of the Tridentate Pyridine-based Ru(Ⅱ) Complex upon the Catalytic Activity in Transfer Hydrogenation[J]. Chin.J.Chem.Eng., 2011, 19(1): 169-172.

参考文献

1 Noyori, R., Ohkuma, T., “Asymmetric catalysis by architectural and functional molecular engineering: Practical chemoand stereoselective hydrogenation of ketones”, Angew. Chem. Int. Ed., 40, 40-73 (2001).

2 B ckval, J.E., “Transition metal hydrides as active intermediates in hydrogen transfer reactions”, J. Organomet. Chem, 652, 105-111 (2002).

3 Noyori, R., Hashiguchi, S., “Asymmetric transfer hydrogenation catalyzed by chiral ruthenium complexes”, Acc. Chem. Res., 30, 97-102 (1997).

4 Koten, G., Dani, P., Karlen, T., Gossage, R.A., Gladiali, S., “Hydrogen-transfer catalysis with pincer-aryl ruthenium (II) complexes”, Angew. Chem., Int. Ed., 39, 743-745 (2000).

5 van de Kuil, L.A., Grove, D.M., Gossage, R.A., Zwikker, J.W., Jenneskens, L.W., Drenth, W., van Koten, G., “Mechanistic aspects of the Kharasch addition reaction catalyzed by organonickel(II) complexes containing the monoanionic terdentate aryldiamine ligand system [C₆H₂(CH₂ NMe₂)₂ -2,6-R-4]”, Organometallics, 16, 4985-4994 (1997).

6 Chanthateyanonth, R., Alper, H., “The first synthesis of stable palladium(II) PCP-type catalysts supported on silica—Application to the Heck reaction”, J. Mol. Catal. A: Chem., 201, 23-31 (2003).

7 Liu, F., Pak, E.B., Singh, B., Jensen, C.M., Goldman, A.S., “Dehydrogenation of n-alkanes catalyzed by iridium “pincer” complexes: Regioselective formation of alpha-olefins”, J. Am. Chem. Soc., 121,4086-4087 (1999).

8 Singleton, J.T., “The uses of pincer complexes in organic synthesis”, Tetrahedron, 59, 1837-1857 (2003).

9 Markies, B.A., Wijkens, P., Boersma, J., Kooijman, H., Veldman, N., Spek, A.L., van Koten, G., “Synthesis and structural studies of ionic monoorganopalladium(II) complexes with tridentate nitrogen-donor ligands”, Organometallics, 13, 3244-3258 (1994).

10 Abbenhuis, R.A.T.M., Boersma, J., van Koten, G., “Rutheniumcomplex-catalyzed N-(cyclo)alkylation of aromatic amines with diols. selective synthesis of N-(ö-hydroxyalkyl)anilines of type PhNH(CH₂)_n OH and of some bioactive arylpiperazines”, J. Org. Chem., 63, 4282-4290 (1998).

11 Gao, H.F., Guo, X.Q., Yang, G., Xu, N.P., “Synthesis and catalytic activities of neutral palladium (II) complexes with tridentate nitrogen ligands”, Chin, J. Org. Chem., 27, 134-137 (2007). (in Chinese)

12 Knapen, J.W.J., van der Made, A.W., de Wilde, J.C., van Leeuwem, B.W.N.M., Wijkens, P., Grove, D.M., van koten, G., “Homogeneous catalysts based on silane dendrimers functionalized with arylnickel (II) complexes”, Nature, 372, 659-663 (1994).

13 Kleij, A.W., Gossage, R.A., Klein Gebbink, R.J.K., Brinkmann, N., Reijerse, E.J., Kragl, U., Lutz, M., van koten, G., Spek, A.L., “A ‘dendritic effect’ in homogeneous catalysis with carbosilane-supported arylnickel (II) catalysts: Observation of active-site proximity effects in atom-transfer radical addition”, J. Am. Chem. Soc., 122, 12112-12124 (2000).

14 Kim, I., Heui, B., Ha, C.S., Kim, J.K., Suh, H., “Preparation of silica-supported bis(imino)pyridyl iron(II) and cobalt(II) catalysts for ethylene polymerization”, Macromolecules, 36, 6689-6691(2003).

15 Zhao, M., Yu, Z.K., Yan, S.G., Li, Y., “Ruthenium(II) complex catalysts bearing a pyridyl-supported pyrazolyl-imine ligand for transfer hydrogenation of ketones”, Journal of Organometallic Chemistry,694, 3068-3075 (2009).

16 Yi, Q.F., Zhang, J.J., Huang, W., Liu, X.P., “Electrocatalytic oxidation of cyclohexanol on a nickel oxyhydroxide modified nickel electrode in alkaline solutions”, Catal. Commun., 8, 1017-1022 (2007).

17 Richel, A., Demonceau, A., Noels, A.F., “Electrochemistry as a correlation tool with the catalytic activities in [RuCl₂ (p-cymene)(PAr₃)]-catalysed Kharasch additions”, Tetrahedron Lett., 47, 2077-2081 (2006).

[1]	储金宇, 仲蕾. 侧光光纤引导的内源可见光催化降解亚甲基蓝[J]. Chinese Journal of Chemical Engineering, 2012, 20(5): 895-899.
[2]	刘颖颖, 鲁厚芳, 蒋炜, 李东升, 刘世界, 梁斌. 微量酸催化麻疯树籽油制备生物柴油[J]. Chinese Journal of Chemical Engineering, 2012, 20(4): 740-746.
[3]	杨青山, 廖永进, 毛玲玲. 气相有机化合物在改性TiO2/AC复合光催化剂上的光催化降解动力学[J]. CIESC Journal, 2012, 20(3): 572-576.
[4]	纪永军, 杨建国. Synthesis of Methyl Isopropyl Ketone and Diethyl Ketone over Ni-Na/ZrO₂-MnO₂-ZnO Catalyst [J]. CIESC Journal, 2011, 19(4): 656-656-660.
[5]	刘其海, 廖列文, 刘自力, 董新法. Effect of ZrO₂ Crystalline Phase on the Performance of Ni-B/ZrO₂ Catalyst for the CO Selective Methanation[J]. CIESC Journal, 2011, 19(3): 434-438.
[6]	刘平, 姚月, 张兴光, 王军. Rare Earth Metals Ion-exchanged β-Zeolites as Supports of Platinum Catalysts for Hydroisomerization of n-Heptane[J]. CIESC Journal, 2011, 19(2): 278-284.
[7]	潘崇根, 李瑛, 蒋文, 刘化章. Effects of Reaction Conditions on Performance of Ru Catalyst and Iron Catalyst for Ammonia Synthesis[J]. CIESC Journal, 2011, 19(2): 273-277.
[8]	舒庆, 高继贤, 廖玉会, 王金福. Reaction Kinetics of Biodiesel Synthesis from Waste Oil Using a Carbon-based Solid Acid Catalyst[J]. CIESC Journal, 2011, 19(1): 163-168.
[9]	朱孝恒, 郭子芳, 岑为, 毛炳权. Ethylene Polymerization Using Improved Polyethylene Catalyst[J]. CIESC Journal, 2011, 19(1): 52-56.
[10]	雷志刚, 龙爱斌, 贾美如, 刘学义. Experimental and Kinetic Study of Selective Catalytic Reduction of NO with NH₃ over CuO/Al₂O₃/Cordierite Catalyst[J]. CIESC Journal, 2010, 18(5): 721-729.
[11]	钱新华, 贾世阳, 苏兴, 陈悦, 王克峰, 姚平经. Adaptive On-line Operation Guide for Dry Gas-to-ethylbenzene Reactor[J]. CIESC Journal, 2010, 18(3): 419-424.
[12]	周志明, 李浔, 曾天鹰, 洪闻彬, 程振民, 袁渭康. Kinetics of Hydrogenolysis of Glycerol to Propylene Glycol over Cu-ZnO-Al₂O₃ Catalysts[J]. CIESC Journal, 2010, 18(3): 384-390.
[13]	白赢, 彭家建, 胡应乾, 厉嘉云, 邱化玉, 来国桥. Effect of Aminoaromatic Acids as Additives on the Activity and Selectivity of the Platinum-catalyzed Hydrosilylation of Alkenes[J]. CIESC Journal, 2009, 17(6): 1038-1042.
[14]	方健才, 陈晓, 夏启斌, 奚红霞, 李忠. Effect of Relative Humidity on Catalytic Combustion of Toluene over Copper Based Catalysts with Different Supports[J]. CIESC Journal, 2009, 17(5): 767-772.
[15]	耿艳楼, 胡利彦, 赵新强, 安华良, 王延吉. Synthesis of 4,4'-MDC in the Presence of Sulfonic Acid-functionalized Ionic Liquids[J]. CIESC Journal, 2009, 17(5): 756-760.

Effect of the Para-substituent of the Tridentate Pyridine-based Ru(Ⅱ) Complex upon the Catalytic Activity in Transfer Hydrogenation

Effect of the Para-substituent of the Tridentate Pyridine-based Ru(Ⅱ) Complex upon the Catalytic Activity in Transfer Hydrogenation

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价