Theoretical Study on the Reaction Mechanism of Hydrolysis Process of Asymmetric trans-[Pt(Ⅱ)Cl2(#em/em#-pra)(hmp)] Complex

Abstract

Abstract: The hydrolysis process of the anticancer drug trans-[Pt(Ⅱ)Cl2(i-pra)(hmp)](i-pra= isopropylamine, hmp= 3-(hydroxylmethyl)-pyridine) with steric hindrance has been investigated by density functional theory at PBE1PBE level and CPCM model. The results exhibited that water molecules attack the Pt and Cl atoms perpendicularly to the quadrangular coordinate plane of Pt due to the steric effect. The hydrolysis is the synergistic effect of the H, O, Cl and Pt atom, acting as the 3p(Cl)→σ*(H-O), 5d(Pt)→σ*(H-O), LP(O)→LP*(Pt) and LP(O)→σ*(Pt-Cl) delocalizations. The transition state is an approximate trigonal-bipyramid geometry. In the processing of hydrolysis, the delocalization effect and the strength of Pt-O bond increase, while the strength of Pt-Cl bond decreases. Due to the solvent effects, energies of every reactant, transition state and product of the first and second hydrolysis are 63.6~386.3 kJ/mol lower than those of the gas phase, and the single-point energy barriers are 17.1~36.2 kJ/mol lower than those of the gas phase. The hydrolysis process is easier in the opposite direction of isopropyl with less steric hindrance. 1B and 2B are the dominant reaction paths of first and second hydrolysis, their enthalpy barrier (ΔH°298(aq)) are 79.7 kJ/mol and 87.8 kJ/mol respectively, which are higher than those of trans-[PtCl2(i-pra)2]. Moreover, the enthalpy barrier of second hydrolysis is much higher than cisplatin.

Key words: trans-Platinum complexes, density functional theory (DFT), hydrolysis reaction, reaction mechanism, solvent effect

TrendMD:

YE Bing, XU Xuan. Theoretical Study on the Reaction Mechanism of Hydrolysis Process of Asymmetric trans-[Pt(Ⅱ)Cl₂(#em/em#-pra)(hmp)] Complex[J]. Chem. J. Chinese Universities, 2010, 31(12): 2431.

share this article

0
/ / Recommend

Add to citation manager EndNote|Ris|BibTeX

URL: http://www.cjcu.jlu.edu.cn/EN/

http://www.cjcu.jlu.edu.cn/EN/Y2010/V31/I12/2431

References

Related Articles 15

[1] ZHOU Zixuan, YANG Haiyan, SUN Yuhan, GAO Peng. Recent Progress in Heterogeneous Catalysts for the Hydrogenation of Carbon Dioxide to Methanol [J]. Chem. J. Chinese Universities, 2022, 43(7): 20220235.

[2] YANG Dan, LIU Xu, DAI Yihu, ZHU Yan, YANG Yanhui. Research Progress in Electrocatalytic CO₂ Reduction Reaction over Gold Clusters [J]. Chem. J. Chinese Universities, 2022, 43(7): 20220198.

[3] SUN Cuihong, LYU Liqiang, LIU Ying, WANG Yan, YANG Jing, ZHANG Shaowen. Mechanism and Kinetics on the Reaction of Isopropyl Nitrate with Cl， OH and NO₃ Radicals [J]. Chem. J. Chinese Universities, 2022, 43(2): 20210591.

[4] CHENG Yuanyuan, XI Biying. Theoretical Study on the Fragmentation Mechanism of CH₃SSCH₃ Radical Cation Initiated by OH Radical [J]. Chem. J. Chinese Universities, 2022, 43(10): 20220271.

[5] MENG Fanwei, GAO Qi, YE Qing, LI Chenxi. Potassium Poisoning Mechanism of Cu-SAPO-18 Catalyst for Selective Catalytic Reduction of NO_x by Ammonia [J]. Chem. J. Chinese Universities, 2021, 42(9): 2832.

[6] YANG Yiying, ZHU Rongxiu, ZHANG Dongju, LIU Chengbu. Theoretical Study on Gold-catalyzed Cyclization of Alkynyl Benzodioxin to 8-Hydroxy-isocoumarin [J]. Chem. J. Chinese Universities, 2021, 42(7): 2299.

[7] LI Xinyi, LIU Yongjun. Theoretical Insights into the Cleavage of β-Hydroxy Ketone Catalyzed by Artificial Retro-aldolase RA95.5-8F [J]. Chem. J. Chinese Universities, 2021, 42(7): 2306.

[8] REN Ying, LI Changhua, WANG Tao, XUE Shanshan, ZHANG Tingting, JIA Jianfeng, WU Haishun. Theoretical Studies on Pd-catalyzed Oxidative N─H Carbonylation to Synthesis of 1，3，4-Oxadiazole-2（3H）-one Heterocyclic Compounds [J]. Chem. J. Chinese Universities, 2021, 42(6): 1793.

[9] LI Yiwei, SHENTU Jiangtao, WANG Jingbo, LI Xiangyuan. Combustion Mechanism Construction Based on Minimized Reaction Network： C1⁃Oxygen Combustion [J]. Chem. J. Chinese Universities, 2021, 42(6): 1871.

[10] TIAN Shengqiao, WEI Meiju. Reaction Mechanism for Rh（Ⅱ）-catalyzed ［3+3］ Cyclization of Indole Derivatives and Propertis of Product [J]. Chem. J. Chinese Universities, 2021, 42(6): 1899.

[11] QI Guodong, YE Xiaodong, XU Jun, DENG Feng. Progress in NMR Studies of Carbohydrates Conversion on Zeolites [J]. Chem. J. Chinese Universities, 2021, 42(1): 148.

[12] LI Xiangyuan, SHENTU Jiangtao, LI Yiwei, LI Juanqin, WANG Jingbo. Combustion Mechanism Construction Based on Minimized Reaction Network: Hydrogen-Oxygen Combustion ^† [J]. Chem. J. Chinese Universities, 2020, 41(4): 772.

[13] LI Xiangyuan,YAO Xiaoxia,SHENTU Jiangtao,SUN Xiaohui,LI Juanqin,LIU Mingxia,XU Shimin. Combustion Reaction Mechanism Construction by Two-parameter Rate Constant Method ^† [J]. Chem. J. Chinese Universities, 2020, 41(3): 512.

[14] ZHANG Lin, ZHANG Wei, YUE Xin, LI Pengjie, YANG Zuoyin, PU Min, LEI Ming. Theoretical Study on Mechanism of CO₂ Hydrogenation to Formic Acid Catalyzed by Manganese Complex ^† [J]. Chem. J. Chinese Universities, 2019, 40(9): 1911.

[15] LI Qing, YI Pinggui, TAO Hongwen, LI Yangyang, ZHANG Zhiyu, PENG Wenyu, LI Yuru. Solvent and Substituent Effects on Spectral Characteristics and Excited-state Intramolecular Proton Transfer of 2-(2-Aminophenyl) Benzothiazole^† [J]. Chem. J. Chinese Universities, 2019, 40(7): 1425.

Recommended Articles

Metrics

Viewed

Full text

Abstract

Comments

Abstract

References

Related Articles

Recommended Articles

Metrics

Comments

TOP

Theoretical Study on the Reaction Mechanism of Hydrolysis Process of Asymmetric trans-[Pt(Ⅱ)Cl₂(#em/em#-pra)(hmp)] Complex

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	ZHOU Zixuan, YANG Haiyan, SUN Yuhan, GAO Peng. Recent Progress in Heterogeneous Catalysts for the Hydrogenation of Carbon Dioxide to Methanol [J]. Chem. J. Chinese Universities, 2022, 43(7): 20220235.
[2]	YANG Dan, LIU Xu, DAI Yihu, ZHU Yan, YANG Yanhui. Research Progress in Electrocatalytic CO₂ Reduction Reaction over Gold Clusters [J]. Chem. J. Chinese Universities, 2022, 43(7): 20220198.
[3]	SUN Cuihong, LYU Liqiang, LIU Ying, WANG Yan, YANG Jing, ZHANG Shaowen. Mechanism and Kinetics on the Reaction of Isopropyl Nitrate with Cl， OH and NO₃ Radicals [J]. Chem. J. Chinese Universities, 2022, 43(2): 20210591.
[4]	CHENG Yuanyuan, XI Biying. Theoretical Study on the Fragmentation Mechanism of CH₃SSCH₃ Radical Cation Initiated by OH Radical [J]. Chem. J. Chinese Universities, 2022, 43(10): 20220271.
[5]	MENG Fanwei, GAO Qi, YE Qing, LI Chenxi. Potassium Poisoning Mechanism of Cu-SAPO-18 Catalyst for Selective Catalytic Reduction of NO_x by Ammonia [J]. Chem. J. Chinese Universities, 2021, 42(9): 2832.
[6]	YANG Yiying, ZHU Rongxiu, ZHANG Dongju, LIU Chengbu. Theoretical Study on Gold-catalyzed Cyclization of Alkynyl Benzodioxin to 8-Hydroxy-isocoumarin [J]. Chem. J. Chinese Universities, 2021, 42(7): 2299.
[7]	LI Xinyi, LIU Yongjun. Theoretical Insights into the Cleavage of β-Hydroxy Ketone Catalyzed by Artificial Retro-aldolase RA95.5-8F [J]. Chem. J. Chinese Universities, 2021, 42(7): 2306.
[8]	REN Ying, LI Changhua, WANG Tao, XUE Shanshan, ZHANG Tingting, JIA Jianfeng, WU Haishun. Theoretical Studies on Pd-catalyzed Oxidative N─H Carbonylation to Synthesis of 1，3，4-Oxadiazole-2（3H）-one Heterocyclic Compounds [J]. Chem. J. Chinese Universities, 2021, 42(6): 1793.
[9]	LI Yiwei, SHENTU Jiangtao, WANG Jingbo, LI Xiangyuan. Combustion Mechanism Construction Based on Minimized Reaction Network： C1⁃Oxygen Combustion [J]. Chem. J. Chinese Universities, 2021, 42(6): 1871.
[10]	TIAN Shengqiao, WEI Meiju. Reaction Mechanism for Rh（Ⅱ）-catalyzed ［3+3］ Cyclization of Indole Derivatives and Propertis of Product [J]. Chem. J. Chinese Universities, 2021, 42(6): 1899.
[11]	QI Guodong, YE Xiaodong, XU Jun, DENG Feng. Progress in NMR Studies of Carbohydrates Conversion on Zeolites [J]. Chem. J. Chinese Universities, 2021, 42(1): 148.
[12]	LI Xiangyuan, SHENTU Jiangtao, LI Yiwei, LI Juanqin, WANG Jingbo. Combustion Mechanism Construction Based on Minimized Reaction Network: Hydrogen-Oxygen Combustion ^† [J]. Chem. J. Chinese Universities, 2020, 41(4): 772.
[13]	LI Xiangyuan,YAO Xiaoxia,SHENTU Jiangtao,SUN Xiaohui,LI Juanqin,LIU Mingxia,XU Shimin. Combustion Reaction Mechanism Construction by Two-parameter Rate Constant Method ^† [J]. Chem. J. Chinese Universities, 2020, 41(3): 512.
[14]	ZHANG Lin, ZHANG Wei, YUE Xin, LI Pengjie, YANG Zuoyin, PU Min, LEI Ming. Theoretical Study on Mechanism of CO₂ Hydrogenation to Formic Acid Catalyzed by Manganese Complex ^† [J]. Chem. J. Chinese Universities, 2019, 40(9): 1911.
[15]	LI Qing, YI Pinggui, TAO Hongwen, LI Yangyang, ZHANG Zhiyu, PENG Wenyu, LI Yuru. Solvent and Substituent Effects on Spectral Characteristics and Excited-state Intramolecular Proton Transfer of 2-(2-Aminophenyl) Benzothiazole^† [J]. Chem. J. Chinese Universities, 2019, 40(7): 1425.