Theoretical Insights into the Actinide-Silicon Bonding Nature and Stability of a Series of Actinide Complexes with Different Oxidation States
文献类型：期刊论文
| 作者 | Li, Ai-Lin; Zhang, Nai-Xin; Wu, Qun-Yan; Wang, Cong-Zhi; Lan, Jian-Hui; Nie, Chang-Ming; Chai, Zhi-Fang; Shi, Wei-Qun |
| 刊名 | ORGANOMETALLICS
 |
| 出版日期 | 2021 |
| 卷号 | 40期号:11页码:1719-1727 |
| 关键词 | METAL-METAL BONDS DENSITY-FUNCTIONAL THEORY ELECTRON LOCALIZATION GROUP-14 ELEMENT COVALENT RADII CHEMICAL-BONDS TH-PU URANIUM REACTIVITY NITRIDE |
| 英文摘要 | The electronic structures of a series of complexes (CpSiMe3)(3)AnSi(NCHMes)(2) ([An-Si], An = Th-Am) with different oxidation states (OS = II, III, and IV) of actinides were investigated using the relativistic density functional theory to explore the actinide-silicon bonding, which was evaluated based on the analyses of quantum theory of atoms in molecules (QTAIM) and electron localization function (ELF). The An-Si bond length variation for a series of [An-Si] with different oxidation states may be attributed to the synergistic effect of the steric hindrance and the ability of the actinide atom to accept electrons. The value of AnSi Mayer bond order (MBO) decreases across the actinide series with the same oxidation state. The values of An-Si MBO for the [An(II)-Si](-) (An = Th-Pu) are the largest in general among the complexes with three actinide oxidation states, except that for the Am-Si MBO of [Am-IV-Si](+) is the largest because of more covalent Am-Si bond in the [Am-IV-Si](+) complex. The An-Si bonds are highly polarized due to lone pair electrons located on the Si 3s orbital. Moreover, the An-Si bonds possess donor-acceptor interactions according to the analyses of QTAIM and ELF. In addition, the binding energies suggest that the tetravalent complexes [An(IV)-Si](+) are accessible, of which [U-IV-Si](+) and [Pu-IV-Si](+) are the most preferable. The electron affinity analysis suggests reaction of [An(III)-Si] -> [An(II)-Si](-) should become increasingly facile across the actinide series from Th to Am. the knowledge on the An-Si bonding, especially for the transuranium-silicon bonding, and guides synthesis of complexes with different oxidation states. |
| 源URL | [http://ir.nimte.ac.cn/handle/174433/21833]  |
| 专题 | 中国科学院宁波材料技术与工程研究所 2021专题_期刊论文 |
| 作者单位 | 1.Shi, WQ (corresponding author), Chinese Acad Sci, Inst High Energy Phys, Lab Nucl Energy Chem, Beijing 100049, Peoples R China. 2.Wu, QY |
| 推荐引用方式 GB/T 7714 | Li, Ai-Lin,Zhang, Nai-Xin,Wu, Qun-Yan,et al. Theoretical Insights into the Actinide-Silicon Bonding Nature and Stability of a Series of Actinide Complexes with Different Oxidation States[J]. ORGANOMETALLICS,2021,40(11):1719-1727. |
| APA | Li, Ai-Lin.,Zhang, Nai-Xin.,Wu, Qun-Yan.,Wang, Cong-Zhi.,Lan, Jian-Hui.,...&Shi, Wei-Qun.(2021).Theoretical Insights into the Actinide-Silicon Bonding Nature and Stability of a Series of Actinide Complexes with Different Oxidation States.ORGANOMETALLICS,40(11),1719-1727. |
| MLA | Li, Ai-Lin,et al."Theoretical Insights into the Actinide-Silicon Bonding Nature and Stability of a Series of Actinide Complexes with Different Oxidation States".ORGANOMETALLICS 40.11(2021):1719-1727. |
入库方式： OAI收割
来源：宁波材料技术与工程研究所
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