title: Molecular structure, IR spectra, and chemical reactivity of cisplatin and transplatin: DFT studies, basis set effect and solvent effect.
abstract: Three different density functional theory (DFT) methods were employed to study the molecular structures of cis-diamminedichloroplatinum(II) (CDDP) and trans-diamminedichloroplatinum(II) (TDDP). The basis set effect on the structure was also investigated. By comparing the optimized structures with the experimental data, a relatively more accurate method was chosen for further study of the IR spectra and other properties as well as the solvent effect. Nineteen characteristic vibrational bands of the title compounds were assigned and compared with available experimental data. The number of characteristic peaks for the asymmetric stretching and deformation vibrations of N-H can serve as a judgment for the isomer between CDDP and TDDP. Significant solvent effect was observed on the molecular structures and IR spectra. The reduced density gradient analysis was performed to study the intramolecular interactions of CDDP and TDDP, and the nature of changes in the structures caused by the solvent was illustrated. Several descriptors determined from the energies of frontier molecular orbitals (HOMO and LUMO) were applied to describe the chemical reactivity of the title compounds. The molecular electrostatic potential (MESP) surfaces showed that the amino groups were the most favorable sites that nucleophilic reagents tend to attack, and CDDP was easier to be attacked by nucleophilic reagents than TDDP.
authors.affiliation: School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, PR China; Key Laboratory of Nuclear Medicine, Ministry of Health & Jiangsu Key Laboratory of Molecular Nuclear Medicine, Jiangsu Institute of Nuclear Medicine, Wuxi 214063, PR China.
authors.forename: Yang
authors.initials: Y
authors.lastname: Wang
authors.affiliation: School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, PR China; Key Laboratory of Nuclear Medicine, Ministry of Health & Jiangsu Key Laboratory of Molecular Nuclear Medicine, Jiangsu Institute of Nuclear Medicine, Wuxi 214063, PR China.
authors.forename: Qingzhu
authors.initials: Q
authors.lastname: Liu
authors.affiliation: Key Laboratory of Nuclear Medicine, Ministry of Health & Jiangsu Key Laboratory of Molecular Nuclear Medicine, Jiangsu Institute of Nuclear Medicine, Wuxi 214063, PR China; School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, PR China. Electronic address: qiuling@jsinm.org.
authors.forename: Ling
authors.initials: L
authors.lastname: Qiu
authors.affiliation: School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, PR China; Key Laboratory of Nuclear Medicine, Ministry of Health & Jiangsu Key Laboratory of Molecular Nuclear Medicine, Jiangsu Institute of Nuclear Medicine, Wuxi 214063, PR China.
authors.forename: Tengfei
authors.initials: T
authors.lastname: Wang
authors.affiliation: Key Laboratory of Nuclear Medicine, Ministry of Health & Jiangsu Key Laboratory of Molecular Nuclear Medicine, Jiangsu Institute of Nuclear Medicine, Wuxi 214063, PR China.
authors.forename: Haoliang
authors.initials: H
authors.lastname: Yuan
authors.affiliation: Key Laboratory of Nuclear Medicine, Ministry of Health & Jiangsu Key Laboratory of Molecular Nuclear Medicine, Jiangsu Institute of Nuclear Medicine, Wuxi 214063, PR China.
authors.forename: Jianguo
authors.initials: J
authors.lastname: Lin
authors.affiliation: Key Laboratory of Nuclear Medicine, Ministry of Health & Jiangsu Key Laboratory of Molecular Nuclear Medicine, Jiangsu Institute of Nuclear Medicine, Wuxi 214063, PR China; School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, PR China. Electronic address: luoshineng@jsinm.org.
authors.forename: Shineng
authors.initials: S
authors.lastname: Luo
mesh_terms: D000970:Antineoplastic Agents / Q000737:chemistry*; D002945:Cisplatin / Q000737:chemistry*; D003432:Cross-Linking Reagents / Q000737:chemistry*; D007536:Isomerism; D008958:Models, Molecular; D011789:Quantum Theory; D012997:Solvents / Q000737:chemistry; D013055:Spectrophotometry, Infrared
chemical_list: D000970:Antineoplastic Agents; D003432:Cross-Linking Reagents; D012997:Solvents; C034697:transplatin; D002945:Cisplatin
keywords: Basis set effect; Chemical reactivity; DFT; Platinum complexes; Solvent effect