Thermokinetic Study of Formation Reaction of N,N,O,O-Tetradentate Ligand-palladium(Ⅱ) Complex and Its Catalytic Performance in Suzuki Reaction

doi:10.7503/cjcu20130031

Abstract

Abstract:

A new N-O ligand 1-(6-chloro-pyridin-2-yl)-5-hydroxy-1H-pyrazole-3-carboxylic acid methyl ester was prepared and structurally analyzed. The solid lattice of the compound at 296 K reveals one dimensional chain structure connected by intermolecular hydrogen bonds [C3—H3…O2, 0.2535(17) nm] and halogen bonds [C1—Cl1…O1, 0.3161(18) nm, Cl atom as Lewis acid and oxygen atom as Lewis base] interactions. The ligand adds to palladium(Ⅱ) to give high yield of air-stable complex 1 that was fully characterized by infrared(IR) spectroscopy, nuclear magnetic resonance(NMR) spectroscopy and high resolution mass spectrum(HRMS). The dynamic thermochemistry for the formation of complex 1 in liquid-phase was explored by a microcalorimeter. Thermodynamic parameters(the activation enthalpy, the activation entropy and the activation free energy), kinetics parameters(the apparent activation energy, the pre-exponential constant and the reaction order) and rate constants of the coordination reaction were procured. Complex 1 was used as catalyst for the Suzuki cross-coupling between different aryl bromides and phenylboronic acid in water/ethanol with KOH as base under microwave irradiation and afforded the corresponding cross-coupled biaryls in 80.7%-95.9% yields. Furthermore, the reactions of aryl chlorides and phenylboronic acid were also successfully achieved in comparable yields.

Key words: Palladium(Ⅱ) complex, Thermodynamic, Suzuki reaction

CLC Number:

O643
O621.1

TrendMD:

SHEN Li-Qun, HUANG Su-Yu, LEI Fu-Hou, HUANG Zai-Yin. Thermokinetic Study of Formation Reaction of N,N,O,O-Tetradentate Ligand-palladium(Ⅱ) Complex and Its Catalytic Performance in Suzuki Reaction[J]. Chem. J. Chinese Universities, 2013, 34(6): 1428.

[1]	REN Nana, XUE Jie, WANG Zhifan, YAO Xiaoxia, WANG Fan. Effects of Thermodynamic Data on Combustion Characters of 1，3-Butadiene [J]. Chem. J. Chinese Universities, 2022, 43(6): 20220151.
[2]	WANG Kun, ZOU Xingli, CAO Zhanmin, LI Chonghe, LU Xionggang. Modified Quasichemical Model for Manifold Short-range Orders in Binary Solutions： Unity of Opposites for the Ordered Pairs [J]. Chem. J. Chinese Universities, 2022, 43(11): 20220391.
[3]	HE Zijun,XIAO Ming,MA Xiangying,QIU Jiangyuan,XIAO Biyuan,QIN Fanghong,HUANG Zaiyin. Facet and Temperature Effects on Dissolution Thermodynamic Functions of Ag₃PO₄ Microcrystals^† [J]. Chem. J. Chinese Universities, 2019, 40(5): 959.
[4]	Yanjie LI,Ensi WANG,Xiaowei SHAO,Xingmin ZHANG,Shengxiu NIU,Lijuan YANG,Yi WU. Synthesis and Biological Activity in vitro of Imidazo[4,5-c]quinoline Derivatives ^† [J]. Chem. J. Chinese Universities, 2019, 40(12): 2502.
[5]	XIAO Biyuan,QIU Jiangyuan,QIN Fanghong,WAN Ting,XU Yaqun,NONG Xiaohui,HUANG Zaiyin. Study on Particle Size Effect on Adsorption Thermodynamics and Kinetics of Cubic Nano-Cu₂O ^† [J]. Chem. J. Chinese Universities, 2019, 40(10): 2214.
[6]	JIANG Tao, WANG Ning, PENG Shuming, LI Mei, HAN Wei, CHEN Yitung. Electrochemical Behaviour of Gd(Ⅲ) on Bi Electrode and Thermodynamic Data of Bi_xGd_y Intermetallic Compounds in LiCl-KCl Molten Salts^† [J]. Chem. J. Chinese Universities, 2018, 39(8): 1759.
[7]	QIN Fanghong,QIU Jiangyuan,XIAO Biyuan,MI Yan,HUANG Zaiyin. Investigation into the Thermodynamic Properties of Nano-silver Halides Based on the Principle of Dissolution Thermodynamics^† [J]. Chem. J. Chinese Universities, 2018, 39(10): 2214.
[8]	YANG Yejin,YOU Jinglin,WANG Jian,WANG Min,HE Yingxia,WU Zhidong. In-situ High Temperature Raman Spectroscopic and Decomposition Thermodynamic Study of the Structure of Potassium Hydrogen Sulfate and Its Melt^† [J]. Chem. J. Chinese Universities, 2018, 39(10): 2272.
[9]	SHI Zhanping, SHI Mai, ZHANG Wenhui, SHEN Shigang, YUE Zhilian, YANG Hui, DING Liang, PAN Xuefeng. Preparation, Characterization and Toxicological Analysis of Alginate-phospholipid Vesicle Composite Hydrogels^† [J]. Chem. J. Chinese Universities, 2017, 38(7): 1270.
[10]	MA Changmin, LIU Tingyu, CHANG Qiuxiang, LUO Guoyin. Theoretical Studies on the Intrinsic Defects in ZnO and ZnS Crystal^† [J]. Chem. J. Chinese Universities, 2016, 37(5): 932.
[11]	ZHOU Wenjun, ZHOU Yu, ZHANG Xiazhong, ZENG Bin. Preparation and Suzuki Reaction Performance of Pectin-supported Palladium Catalyst^† [J]. Chem. J. Chinese Universities, 2016, 37(4): 669.
[12]	LIU Zuojiao, FAN Gaochao, HE Liangming, DIAO Kaisheng, HUANG Zaiyin, TAN Xuecai. Temperature and Morphology Effect on Surface Thermodynamic Functions of Ag₃PO₄ Microcrystals^† [J]. Chem. J. Chinese Universities, 2015, 36(7): 1385.
[13]	SHEN Gangyi, GAO Yan, ZHANG Aiqin, CUI Jian, DAI Dongsheng. Thermodynamic Study of Chiral Recognition Between Serum Albumin and Tryptophan Enantiomers by Surface Plasmon Resonance^† [J]. Chem. J. Chinese Universities, 2015, 36(5): 881.
[14]	LIU Xiaolin, WANG Lude, HUANG Zaiyin, LIU Zuojiao, LI Xingxing. Thermodynamic Functions of Nano Zinc Oxide Acquired by Microcalorimetry and Electrochemical Methods^† [J]. Chem. J. Chinese Universities, 2015, 36(3): 539.
[15]	LIU Zuojiao, FAN Gaochao, LI Xingxing, TAN Xuecai, ZHONG Lianyun, HUANG Zaiyin. Thermodynamic and Kinetic Parameters of in-situ Photocatalytic Process with Different Morphologies of Ag₃PO₄ and Their Free Energy^† [J]. Chem. J. Chinese Universities, 2015, 36(2): 212.

Thermokinetic Study of Formation Reaction of N,N,O,O-Tetradentate Ligand-palladium(Ⅱ) Complex and Its Catalytic Performance in Suzuki Reaction

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments