| DOI | 10.1038/s41586-020-2004-7
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| Actinide 2-metallabiphenylenes that satisfy Huckel's rule |
| Achar, Yathish Jagadheesh1; Adhil, Mohamood1; Choudhary, Ramveer1; Gilbert, Nick2; Foiani, Marco1,3
|
| 2020-01-30
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| 发表期刊 | NATURE
 |
| ISSN | 0028-0836
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| EISSN | 1476-4687
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| 出版年 | 2020
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| 卷号 | 578期号:7796页码:563-+ |
| 文章类型 | Article
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| 语种 | 英语
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| 国家 | USA; Peoples R China |
| 英文关键词 | Aromaticity and antiaromaticity, as defined by Huckel'
s rule, are key ideas in organic chemistry, and are both exemplified in biphenylene(1-3)-a molecule that consists of two benzene rings joined by a four-membered ring at its core. Biphenylene analogues in which one of the benzene rings has been replaced by a different (4n + 2) pi-electron system have so far been associated only with organic compounds(4,5). In addition, efforts to prepare a zirconabiphenylene compound resulted in the isolation of a bis(alkyne) zirconocene complex instead(6). Here we report the synthesis and characterization of, to our knowledge, the first 2-metallabiphenylene compounds. Single-crystal X-ray diffraction studies reveal that these complexes have nearly planar, 11-membered metallatricycles with metrical parameters that compare well with those reported for biphenylene. Nuclear magnetic resonance spectroscopy, in addition to nucleus-independent chemical shift calculations, provides evidence that these complexes contain an antiaromatic cyclobutadiene ring and an aromatic benzene ring. Furthermore, spectroscopic evidence, Kohn-Sham molecular orbital compositions and natural bond orbital calculations suggest covalency and delocalization of the uranium f(2) electrons with the carbon-containing ligand.
The synthesis of uranium- and thorium-containing metallabiphenylenes demonstrates the ability of the actinides to stabilize aromatic/antiaromatic structures where transition metals have failed.
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| 领域 | 地球科学
; 气候变化
; 资源环境
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| 收录类别 | SCI-E
|
| WOS记录号 | WOS:000516571100017
|
| WOS关键词 | 2ND-ORDER PERTURBATION-THEORY
; MOLECULAR-ORBITAL METHODS
; BASIS-SETS
; ELECTRONIC-STRUCTURE
; HALIDE-COMPLEXES
; THERMOCHEMISTRY
; PHENYLSILANE
; AROMATICITY
; THORIUM(IV)
; REACTIVITY
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| WOS类目 | Multidisciplinary Sciences
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| WOS研究方向 | Science & Technology - Other Topics
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| 引用统计 |
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| 文献类型 | 期刊论文
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| 条目标识符 | http://119.78.100.173/C666/handle/2XK7JSWQ/281414
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| 专题 | 地球科学
资源环境科学
气候变化
|
| 作者单位 | 1.IFOM Fdn Ist FIRC Oncol Mol, Milan, Italy;
2.Univ Edinburgh, Inst Genet & Mol Med, Med Res Council, Human Genet Unit, Edinburgh, Midlothian, Scotland;
3.Univ Milan, Milan, Italy
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推荐引用方式
GB/T 7714 |
Achar, Yathish Jagadheesh,Adhil, Mohamood,Choudhary, Ramveer,et al. Actinide 2-metallabiphenylenes that satisfy Huckel's rule[J].
NATURE,2020,578(7796):563-+.
|
| APA |
Achar, Yathish Jagadheesh,Adhil, Mohamood,Choudhary, Ramveer,Gilbert, Nick,&Foiani, Marco.(2020).Actinide 2-metallabiphenylenes that satisfy Huckel's rule.NATURE,578(7796),563-+.
|
| MLA |
Achar, Yathish Jagadheesh,et al."Actinide 2-metallabiphenylenes that satisfy Huckel's rule".NATURE 578.7796(2020):563-+.
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