Tetrapositive Hafnium-Diamide Complexes in the Gas Phase: Formation, Structure and Reaction
文献类型：期刊论文
| 作者 | Chen, XT; Gong, Y |
| 刊名 | JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY
 |
| 出版日期 | 2019 |
| 卷号 | 30期号:12页码:2623-2631 |
| 关键词 | MOLECULAR-ORBITAL METHODS MULTIPLY-CHARGED IONS METAL TRICATIONS BASIS-SETS COORDINATION CHEMISTRY DISSOCIATION STABILITY ZIRCONIUM ELEMENTS |
| ISSN号 | 1044-0305 |
| DOI | 10.1007/s13361-019-02328-x |
| 文献子类 | 期刊论文 |
| 英文摘要 | Tetrapositive hafnium complexes in the form of Hf(TMPDA)(3)(4+) and Hf(TMOGA)(3)(4+) were produced by ESI of acetonitrile solutions of Hf(ClO4)(4)/TMPDA and Hf(ClO4)(4)/TMOGA respectively. Analogous Hf(TMGA)(3)(4+) and Hf(TMTDA)(3)(4+) were not observed when the Hf(ClO4)(4)/TMGA and Hf(ClO4)(4)/TMTDA solutions were subjected to ESI under similar conditions. Geometry optimizations on these four tetrapositive complexes revealed that the Hf(TMPDA)(3)(4+) and Hf(TMOGA)(3)(4+) complexes possess C-3 and D-3 geometries respectively with the Hf4+ center coordinated by nine atoms. Similar geometries were found for Hf(TMGA)(3)(4+) and Hf(TMTDA)(3)(4+), but both are six-coordinate complexes, which should account for their absence in the gas phase. In addition, no tetrapositive hafnium ion was observed when methanol was used as a solvent instead of acetonitrile. The much stronger affinity of Cl- toward Hf4+ than ClO4- should be the reason why tetrapositive hafnium ions were not observed when HfCl4 was used as the hafnium source. CID of the Hf(TMPDA)(3)(4+) and Hf(TMOGA)(3)(4+) complexes resulted in the formation of Hf(TMPDA)(TMPDA-H)(3+) and Hf(TMOGA)(TMOGA-H)(3+) respectively as the major products. The most stable structures of both tripositive hafnium products arise from the deprotonation of CH3 cis to O-carbonyl, and the Hf(IV) center in both cases is six coordinate. Compared with the loss of protonated ligand observed in the experiments, it is much higher in energy for either Hf(TMPDA)(3)(4+) or Hf(TMOGA)(3)(4+) to lose neutral or cationic ligand on the basis of DFT calculations. |
| 语种 | 英语 |
| 源URL | [http://ir.sinap.ac.cn/handle/331007/32239]  |
| 专题 | 上海应用物理研究所_中科院上海应用物理研究所2011-2017年 |
| 作者单位 | 1.Chinese Acad Sci, Shanghai Inst Appl Phys, Dept Radiochem, Shanghai 201800, Peoples R China; 2.Univ Chinese Acad Sci, Sch Nucl Sci & Technol, Beijing 100049, Peoples R China |
| 推荐引用方式 GB/T 7714 | Chen, XT,Gong, Y. Tetrapositive Hafnium-Diamide Complexes in the Gas Phase: Formation, Structure and Reaction[J]. JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY,2019,30(12):2623-2631. |
| APA | Chen, XT,&Gong, Y.(2019).Tetrapositive Hafnium-Diamide Complexes in the Gas Phase: Formation, Structure and Reaction.JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY,30(12),2623-2631. |
| MLA | Chen, XT,et al."Tetrapositive Hafnium-Diamide Complexes in the Gas Phase: Formation, Structure and Reaction".JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY 30.12(2019):2623-2631. |
入库方式： OAI收割
来源：上海应用物理研究所
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