Knowledge Management System Of Guangzhou Institute of Energy Conversion, CAS
| Aquation and dimerization of osmium(II) anticancer complexes: a density functional theory study | |
| Wang, Hanlu1; De Yonker, Nathan J.2; Gao, Hui3; Tan, Caiping1; Zhang, Xiting1; Ji, Liangnian1; Zhao, Cunyuan1; Mao, Zong-Wan1 | |
| 2012 | |
| Source Publication | RSC ADVANCES
 |
| Volume | 2Issue:2Pages:436-446 |
| Abstract | 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. |
| Subtype | Article |
| WOS Headings | Science & Technology ; Physical Sciences |
| DOI | 10.1039/c1ra00604e |
| WOS Subject Extended | Chemistry |
| WOS Keyword | EFFECTIVE CORE POTENTIALS ; POLARIZABLE CONTINUUM MODEL ; COMPOUND NAMI-A ; DRUG CISPLATIN ; DNA-BINDING ; MOLECULAR CALCULATIONS ; PLATINUM COMPOUNDS ; HYDROLYSIS PROCESS ; ARENE COMPLEXES ; RUTHENIUM COMPLEXES |
| Indexed By | SCI |
| Language | 英语 |
| WOS Subject | Chemistry, Multidisciplinary |
| WOS ID | WOS:000299087000013 |
| Citation statistics | |
| Document Type | 期刊论文 |
| Identifier | http://ir.giec.ac.cn/handle/344007/10554 |
| Collection | 中国科学院广州能源研究所 |
| Affiliation | 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 |
| Recommended Citation 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. |
| Files in This Item: | There are no files associated with this item. | |||||
Items in the repository are protected by copyright, with all rights reserved, unless otherwise indicated.
Edit Comment