Aquation and dimerization of osmium(II) anticancer complexes: a density functional theory study

doi:10.1039/c1ra00604e

GIEC OpenIR > 中国科学院广州能源研究所

	Aquation and dimerization of osmium(II) anticancer complexes: a density functional theory study
	Wang, Hanlu 1; De Yonker, Nathan J.2; Gao, Hui 3; Tan, Caiping 1; Zhang, Xiting 1; Ji, Liangnian 1; Zhao, Cunyuan 1; Mao, Zong-Wan 1
	2012
发表期刊	RSC ADVANCES
卷号	2 期号:2 页码:436-446
摘要	In this paper, the hydrolytic and aqueous solution chemistry of two half-sandwich Os-II arene complexes [(eta(6)-p-cym)Os(pic)Cl] (1) and [(eta(6)-p-cym)Os(mal)Cl] (2) (pic = 2-picolinic acid and mal = maltolate) have been investigated using density functional theory (DFT). For aquation (substitution of chloride by H2O) of the complexes, three attacking models were explored, including two forms of side attack (A and B) and back attack C. Side attack A required the lowest free energy of activation of the three, both in the gas phase and in aqueous solution, suggesting that it best describes the hydrolysis of the complexes. Both the activation and reaction energies indicated faster aquation for 2 than 1, which was in accordance with previous experimental observations. With the side attack model of the complexes, it was found that the conformations of complexes had little effect on the aquation process. Moreover, mechanistic pathways have been obtained for the dimerization of aqua adducts. As for 1a, the ligand departure was the rate-determining step with an activation free energy of 26.1 kcal mol(-1), while for 2a, the first step of ring opening and protonation is rate-determining with a free energy of activation of 24.8 kcal mol(-1), suggesting that 1a was kinetically more stable toward dimerization. There were three factors presented to explain the stability of 1a: differences in HOMO/LUMO densities, the large activation energy of 1a, and stabilization of Os-pic bonding. This study assists in understanding the aqueous solution chemistry of the anticancer complexes and in the design of novel anticancer drugs.
文章类型	Article
WOS标题词	Science & Technology ; Physical Sciences
DOI	10.1039/c1ra00604e
研究领域[WOS]	Chemistry
关键词[WOS]	EFFECTIVE CORE POTENTIALS ; POLARIZABLE CONTINUUM MODEL ; COMPOUND NAMI-A ; DRUG CISPLATIN ; DNA-BINDING ; MOLECULAR CALCULATIONS ; PLATINUM COMPOUNDS ; HYDROLYSIS PROCESS ; ARENE COMPLEXES ; RUTHENIUM COMPLEXES
收录类别	SCI
语种	英语
WOS类目	Chemistry, Multidisciplinary
WOS记录号	WOS:000299087000013
引用统计	被引频次：15[WOS] [WOS记录] [WOS相关记录]
文献类型	期刊论文
条目标识符	http://ir.giec.ac.cn/handle/344007/10554
专题	中国科学院广州能源研究所
作者单位	1.Sun Yat Sen Univ, MOE Key Lab Bioinorgan & Synthet Chem KLGHEI Envi, Sch Chem & Chem Engn, Guangzhou 510275, Guangdong, Peoples R China 2.Univ Memphis, Dept Chem, Memphis, TN 38152 USA 3.Chinese Acad Sci, Guangzhou Inst Energy Convers, Key Lab Renewable Energy & Gas Hydrate, Guangzhou 510640, Peoples R China
推荐引用方式 GB/T 7714	Wang, Hanlu,De Yonker, Nathan J.,Gao, Hui,et al. Aquation and dimerization of osmium(II) anticancer complexes: a density functional theory study[J]. RSC ADVANCES,2012,2(2):436-446.
APA	Wang, Hanlu.,De Yonker, Nathan J..,Gao, Hui.,Tan, Caiping.,Zhang, Xiting.,...&Mao, Zong-Wan.(2012).Aquation and dimerization of osmium(II) anticancer complexes: a density functional theory study.RSC ADVANCES,2(2),436-446.
MLA	Wang, Hanlu,et al."Aquation and dimerization of osmium(II) anticancer complexes: a density functional theory study".RSC ADVANCES 2.2(2012):436-446.